CN110408896A - Substrate with transparent conductive film, manufacturing apparatus and method thereof, and solar cell - Google Patents

Abstract

The invention discloses a substrate with a transparent conductive film, its manufacturing equipment and method, and a solar cell. The substrate with a transparent conductive film includes a third temperature control device for heat-treating the substrate placed on the tray, and a third temperature control device for forming a first transparent conductive film and a second transparent conductive film on the front side and the back side of the substrate, respectively. A film forming device and a second film forming device. In the vicinity of the first target in the film-forming chamber, the gas outlet of the first process gas introduction mechanism is disposed at a position where the first process gas is ejected toward the left target among the first targets in the moving direction of the substrate. In the vicinity of the second target in the film-forming chamber, a gas lead-out portion of the second process gas introduction mechanism is arranged. The first target and the second target are arranged in the film forming chamber, so that a first transparent conductive film is formed on the front side of the substrate by sputtering when the substrate passes in front of the first target, and a first transparent conductive film is formed on the front side of the substrate by sputtering when the substrate passes in front of the second target. The second transparent conductive film is formed on the back side of the substrate by the radiation method.

Description

Substrate with transparent conductive film, manufacturing apparatus and method thereof, and solar cell

technical field

The present invention relates to a manufacturing apparatus of a substrate with a transparent conductive film, a method of manufacturing a substrate with a transparent conductive film, a substrate with a transparent conductive film, and a solar energy Battery.

Background technique

In recent years, solar cells having a heterojunction between crystalline silicon and amorphous silicon (a-Si) (heterojunction-type crystalline Si solar cells) have higher conversion efficiency than conventional crystalline silicon solar cells, and thus have received a lot of attention. Attention. In a heterojunction crystalline Si solar cell, a transparent conductive oxide (TCO) is usually formed on amorphous silicon disposed on both sides of the crystalline silicon. Here, TCO is a transparent and electrically conductive material, and examples thereof include indium oxide, tin oxide, zinc oxide, and the like.

In particular, the TCO arranged on the light-receiving surface side of the solar cell is required to satisfy both low resistance and high transmittance. As one solution to this problem, a solar cell in which a hydrogen-containing transparent conductive film is provided on the light-receiving surface side is known (Patent Document 1).

However, from the viewpoint of the solar cell device, there are problems in that H 2 O is generated due to the contact of the amorphous silicon (a-Si) constituting the substrate of the TCO with the hydrogen-containing plasma, and the H ₂ O is reattached due to the H ₂ O On the amorphous silicon (a-Si), an insulating layer is generated on the interface between the amorphous silicon (a-Si) and the TCO deposited on the amorphous silicon (a-Si). Since the presence of such an insulating layer is a major factor hindering electrical flow in the direction of lamination, there is an urgent need to develop a solution to this problem.

Patent Document 1: Patent International Application Publication No. 2013/061637

SUMMARY OF THE INVENTION

The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a manufacturing apparatus of a substrate with a transparent conductive film, which is formed by arranging transparent conductive films having different hydrogen contents on the front side and the back side of a substrate, and a substrate with a transparent conductive film. A method for producing a substrate, a substrate with a transparent conductive film, and a solar cell.

The manufacturing facility of the substrate with a transparent conductive film according to the first aspect of the present invention includes a film formation chamber including a third temperature adjustment device, a first film formation device, and a second film formation device, and the third temperature adjustment device pair is placed on the The substrate in the state of the tray is subjected to heat treatment, the first film forming apparatus and the second film forming apparatus form a first transparent conductive film and a second transparent conductive film on the front side and the back side of the substrate, respectively, A first process gas for supplying a first process gas containing hydrogen is introduced in the vicinity of a first target in the film-forming chamber that configures the first film-forming apparatus and forms a first transparent conductive film on the front side of the substrate The gas lead-out portion of the mechanism is disposed at a position where the first process gas is ejected to the target located on the left (upper-hand side) of the first targets in the moving direction of the substrate, in the film forming chamber In the vicinity of the second target for constructing the second film forming apparatus and forming the second transparent conductive film on the back side of the substrate, a second process gas introduction mechanism for supplying the second process gas not containing hydrogen is arranged In the gas lead-out portion, the first target and the second target are arranged in the film forming chamber, and when the substrate passes the front surface of the first target, a surface of the substrate is formed with a sputtering method. The first transparent conductive film is formed, and the second transparent conductive film is formed on the back side of the substrate by a sputtering method when the substrate passes through the front surface of the second target.

In the manufacturing apparatus of the substrate with a transparent conductive film according to the first aspect of the present invention, in the film forming chamber, the internal space between the first target and the second target may communicate with each other. One or more exhaust devices having intake ports are arranged.

In the manufacturing facility for a substrate with a transparent conductive film according to the first aspect of the present invention, the tray may include an opening for exposing the front and rear surfaces of the base and a portion for supporting a side surface of the base. In the film chamber, a plurality of the trays are arranged in a line along the traveling direction of the trays, and a specific tray among the plurality of trays has a running direction on the specific tray when passing in front of the first target and the second target. A portion overlapping in the direction with the preceding pallet and the succeeding pallet located before and after the specific pallet, when the specific pallet is viewed from the first target side or the second target side, the specific pallet and the The preceding and succeeding pallets before and after the specific pallet form a set, and the manufacturing facility includes a device for controlling the movement of each pallet so that the preceding and succeeding pallets sandwich the specific pallet on the same surface.

In the manufacturing facility of the substrate with a transparent conductive film according to the first aspect of the present invention, in the film forming chamber, the substrate may be located at a position before the substrate passes through the front surfaces of the first target and the second target. The inner space of each of the inner spaces and the inner spaces located at the positions where film formation passes through the front surfaces of the respective targets, each of the inner spaces is provided with one or more of the third temperature adjustment devices.

In the manufacturing facility of the substrate with a transparent conductive film according to the first aspect of the present invention, the gas of the first process gas introduction means for supplying the first process gas containing hydrogen may be used in the film formation chamber. The lead-out portion is disposed at a position where the first process gas is ejected toward a discharge space that generates a first target that constitutes the first film forming apparatus and forms a first transparent conductive film on the front side of the substrate and the moving substrate.

In the manufacturing facility for a substrate with a transparent conductive film according to the first aspect of the present invention, a flue may be disposed in the film forming chamber so as to surround a discharge space generated in the first structure. The film forming apparatus forms between the first target of the first transparent conductive film and the moving base on the front side of the base.

In the manufacturing facility of the substrate with a transparent conductive film according to the first aspect of the present invention, a loading chamber having a first temperature adjusting device and a heating chamber having a second temperature adjusting device may be provided in the preceding stage of the film forming chamber. The first temperature control device heat-treats the substrate introduced from the atmosphere and placed on the tray in a reduced-pressure atmosphere, and a-Si is disposed on the front and back surfaces, and the second temperature control device heats the substrate from the atmosphere. The trays and substrates moved from the loading chamber are subjected to heat treatment, and a transport chamber and an extraction chamber are provided at the rear stage of the film forming chamber, and the transport chambers cool the trays and substrates moved from the film forming chamber, The extraction chamber leads out the tray and the substrate moved from the transport chamber from the reduced pressure atmosphere to the atmospheric atmosphere.

The method for manufacturing a substrate with a transparent conductive film according to the second aspect of the present invention uses the equipment for manufacturing a substrate with a transparent conductive film according to the first aspect, which includes at least a loading chamber, a heating chamber, a film forming chamber, a transport chamber, and an extraction chamber. A transparent conductive film is formed on the a-Si film disposed on the front and back surfaces of a substrate placed on a tray, and the maximum value of the heat treatment temperature in the loading chamber is defined as T _L [°C] , where the maximum value of the heat treatment temperature in the heating chamber is defined as T _H [°C], and the maximum value of the heat treatment temperature in the film formation chamber is defined as T _SP [°C], T _L ≥ T _SP , or a relational expression of _TH ≥ T _SP .

In the method for producing a substrate with a transparent conductive film according to the second aspect of the present invention, the inner space of the loading chamber and the inner space of the heating chamber may be arranged on the front side and the back side of the base, respectively. The first temperature regulating device and the second temperature regulating device on the side are used for heat treatment of the substrate.

In the method for producing a substrate with a transparent conductive film according to the second aspect of the present invention, the inner space at a position before the substrate passes through the front surface of the first target in the film forming chamber and the The base body is heat-treated by the third temperature control device arranged on the non-film-forming surface side of the base body in the inner space at the position where the base body passes through the front surface of the first target to form a film.

In the method for producing a substrate with a transparent conductive film according to the second aspect of the present invention, the inner space in the film forming chamber at a position before the substrate passes through the front surface of the second target and the inner space in the film formation chamber may be used. The base body is heat-treated by the third temperature control device arranged on the non-film-forming surface side of the base body in the inner space at the position where the base body passes through the front surface of the second target to form a film.

The substrate with a transparent conductive film according to the third aspect of the present invention is a substrate formed by disposing a first transparent conductive film and a second transparent conductive film on the a-Si films disposed on the front surface and the back surface of the base, respectively. The hydrogen content contained in the first transparent conductive film is defined as _CH1 [atoms/cm ³ ], and the hydrogen content contained in the second transparent conductive film is defined as _CH2 [atoms/cm ³ ] In the case of , the relational expression of _CH1 > _CH2 is satisfied.

In the substrate with a transparent conductive film according to the third aspect of the present invention, the _CH1 is on the order of 10 ²¹ (table), and the _CH 2 [number of atoms/cm ³ ] is on the order of 10 ²⁰ .

The solar cell according to the fourth aspect of the present invention includes a substrate with a transparent conductive film obtained by arranging a first transparent conductive film and a second transparent conductive film on a-Si arranged on the front and rear surfaces of the base, respectively. The front side of the substrate is set as the light incident surface, the hydrogen content contained in the first transparent conductive film is defined as C _H1 [atomic number/cm ³ ], and the hydrogen contained in the second transparent conductive film is defined as C H1 [atomic number/cm 3 ]. When the hydrogen content is defined as _CH2 [atomic number/cm ³ ], the relational expression of _CH1 > _CH2 is satisfied.

In the solar cell according to the fourth aspect of the present invention, the _CH1 is of the order of 10 ²¹ , and the _CH 2 [number of atoms/cm ³ ] is of the order of 10 ²⁰ .

According to the method for producing a substrate with a transparent conductive film (hereinafter, also referred to as TCO) according to the above aspect of the present invention, the first film-forming apparatus uses the first target and the hydrogen-containing process gas in a specific interior of the film-forming chamber located in the preceding stage. The first transparent conductive film was formed on the front side of the base body by a sputtering method in space. Next, the second film-forming apparatus forms a second transparent conductive film on the backside of the substrate by sputtering in a specific inner space located in the rear stage of the film-forming chamber using a second target and a hydrogen-free process gas. In other words, the manufacturing apparatus of the present invention can form the hydrogen-containing first transparent conductive film on the front side of the substrate in the specific film-forming space existing in the same film-forming chamber but located at the front stage in the traveling direction of the substrate, after forming the first transparent conductive film containing hydrogen on the front side of the substrate. The second transparent conductive film that does not contain hydrogen is formed on the back side of the base in the specific film-forming space in the latter stage.

Therefore, in the above-described manufacturing facility of the present invention, a substrate of amorphous silicon (a-SI) constituting a TCO base is previously provided on both the front and back sides of the base, and a hydrogen-containing process gas is used to form the first substrate on the front side of the substrate. In the case of a transparent conductive film, even if H ₂ O is generated due to contact with hydrogen-containing plasma, the following problem can be solved: that is, the H ₂ O is wound into the back side of the substrate and reattached to the back side of the substrate. On amorphous silicon (a-Si) or the like, an insulating layer is formed on the interface between the amorphous silicon (a-Si) on the backside of the substrate and the TCO deposited on the amorphous silicon (a-Si).

Therefore, the present invention provides a manufacturing facility that contributes to the formation of a substrate with a transparent conductive film in which transparent conductive films having different hydrogen contents are arranged on the front side and the back side of the substrate.

The method for producing a substrate with a transparent conductive film according to the above aspect of the present invention uses a production facility for a substrate with a transparent conductive film including at least a loading chamber, a heating chamber, a film forming chamber, a conveying chamber, and an extraction chamber. The heat treatment is performed in the loading chamber and the heating chamber in advance before forming a transparent conductive film on the a-Si film disposed on the front and back surfaces of the substrate placed on the tray while the heat treatment is performed in the chamber.

Regarding the heat treatment conditions at this time, the maximum value of the heat treatment temperature in the charging chamber is defined as _TL [°C], the maximum value of the heat treatment temperature in the heating chamber is defined as TH [°C], and the maximum value of the heat treatment temperature in the heating chamber is defined as _TH [°C]. When the maximum value of the heat treatment temperature in the film formation chamber is defined as T _SP [° C.], the relational expression of T _L ≥T _SP or T _H ≥ T _SP is satisfied.

In order to satisfy this relational expression, by controlling the maximum value of each heat treatment temperature in the loading chamber, the heating chamber, and the film forming chamber, the substrate placed on the tray is placed in the loading chamber and the heating chamber located in the preceding stage of the film forming chamber. Welcome to peak temperature. The substrate placed on the tray moved to the film-forming chamber is in a temperature state lower than the peak temperature. Thereby, release and carry-in of water in the film-forming chamber due to the substrate placed on the tray are reduced.

Therefore, according to the method for producing a substrate with a transparent conductive film according to the above aspect of the present invention, since the release and entrainment of water in the film forming chamber are reduced, it is possible to stably form a substrate with different hydrogen contents on the front side and the back side of the substrate. A substrate with a transparent conductive film made of a transparent conductive film.

According to the above-described manufacturing equipment and manufacturing method of the aspect of the present invention, a tape transparent conductive film formed by disposing the first transparent conductive film and the second transparent conductive film on the a-Si films disposed on the front and rear surfaces of the substrate, respectively, is formed. A substrate with a conductive film can be obtained as a substrate with a transparent conductive film: that is, in the substrate with a transparent conductive film, the hydrogen content contained in the first transparent conductive film is defined as C _H1 [atomic number/cm ³ ], When the hydrogen content contained in the second transparent conductive film is defined as _CH2 [number of atoms/cm ³ ], the relational expression of _CH1 > _CH2 is satisfied. Accordingly, the transparent conductive film-coated substrate of the above-described aspect of the present invention has a structure in which transparent conductive films having different hydrogen contents are arranged on the front side and the back side of the base, and the front side of the base can be used as a light incident surface , so it is suitable for solar cell applications.

According to the manufacturing facility and the manufacturing method of the aspect of the present invention described above, it is possible to obtain a transparent conductive tape in which the first transparent conductive film and the second transparent conductive film are respectively provided on the a-Si films provided on the front and back surfaces of the substrate. film substrate. By using this substrate with a transparent conductive film, a solar cell can be obtained in which the front side of the substrate is set as a light incident surface and the hydrogen content contained in the first transparent conductive film is defined When the hydrogen content contained in the second transparent conductive film is defined as _CH1 [atomic number/cm ³ ] and the _hydrogen content contained in the second transparent conductive film is defined as CH 2 [atomic number/cm ³ ], the relational expression of _CH1 > _CH2 is satisfied. The solar cell having this structure can improve the fill factor (FF: Fill Factor) and the power generation efficiency (Eff). In addition, the fill factor is "the value obtained by dividing the maximum output power (Pmax) by the product of the open-circuit voltage (Voc) and the short-circuit current (Isc)", and the power generation efficiency is "the open-circuit voltage (Voc), the short-circuit current density (Jsc) and the Product of Fill Factor (FF)".

Description of drawings

FIG. 1 is a cross-sectional view showing an example of a manufacturing facility for a substrate with a transparent conductive film.

FIG. 2 is a cross-sectional view showing an example of a base body placed on a tray.

3 is an enlarged cross-sectional view showing a gas lead-out portion in a configuration example having two targets.

4 is an enlarged cross-sectional view showing a gas lead-out portion in a configuration example having three targets.

5 is a cross-sectional view showing an example of a substrate with a transparent conductive film and a solar cell including the substrate with a transparent conductive film.

6 is a flowchart showing a conventional method for producing a substrate with a transparent conductive film.

7 is a flowchart showing a method for producing a substrate with a transparent conductive film according to an embodiment of the present invention.

FIG. 8 is a table showing tray temperatures in Examples 1 to 4 of the present invention.

9 is a graph showing tray temperatures in Examples 1 to 4 of the present invention.

FIG. 10 is a graph showing the hydrogen content distribution of the transparent conductive film (in the case of H ₂ O/Ar=0%).

FIG. 11 is a graph showing the hydrogen content distribution of the transparent conductive film (in the case of H ₂ O/Ar=6%).

Detailed ways

Hereinafter, the best mode of the manufacturing facility and manufacturing method of the substrate with a transparent conductive film of the present invention will be described based on the drawings. In addition, the present embodiment is a specific description for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.

<First Embodiment>

Next, referring to FIG. 5 , the production of a substrate with a transparent conductive film in which a transparent conductive film is arranged on a substrate covered with an a-Si film on both the front and back surfaces so as to cover the a-Si film method is explained.

5 is a cross-sectional view showing an example of a substrate with a transparent conductive film and a solar cell including the substrate with a transparent conductive film.

In FIG. 5 , the base 101 (substrate) constituting the substrate with transparent conductive film 10A ( 10 ) is a flat crystalline silicon base material, and both the front 101 a and the back 101 b of the base 101 are covered with a-Si film. In FIG. 5 , the (downward) arrow toward the front surface 101 a of the base body 101 indicates the light incident direction.

The a-Si film (marked as α in FIG. 5 ) provided on the front surface 101a as the light incident side consists of the i-type a-Si film 102 provided in contact with the front surface 101a and the i-type a-Si film 102 provided on the i-type a-Si film 102 p-type a-Si film 103 on the structure. In addition, the first transparent conductive film 104 is provided so as to cover the p-type a-Si film 103 on which the outer surface of the a-Si film (α) is formed. Further, on the outer surface of the first transparent conductive film 104, an electrode 105 formed of a metal film is disposed.

On the other hand, the a-Si film (indicated as β in FIG. 5 ) provided on the back surface 101b which is the non-light incident side consists of the i-type a-Si film 112 provided in contact with the back surface 101b and the a-Si film 112 provided on the back surface 101b. The n-type a-Si film 113 on the i-type a-Si film 112 is structured. In addition, a second transparent conductive film 114 is provided so as to cover the n-type a-Si film 113 on which the outer surface of the a-Si film (β) is formed. Further, on the outer surface of the second transparent conductive film 114, an electrode 115 formed of a metal film is arranged.

In this invention, the hydrogen content contained in the 1st transparent conductive film 104 and the 2nd transparent conductive film 114 is controlled by the manufacturing apparatus and manufacturing method of the board|substrate with a transparent conductive film mentioned later. That is, the hydrogen content contained in the first transparent conductive film 104 is defined as _CH1 [atomic number/cm ³ ], and the hydrogen content contained in the second transparent conductive film is defined as _CH2 [atomic number/cm 3 ] cm ³ ], it is controlled so as to satisfy the relational expression of _CH1 > _CH2 . Thus, the substrate with a transparent conductive film of the present invention has a structure in which transparent conductive films having different hydrogen contents are arranged on the front side and the back side of the base, and the substrate with a transparent conductive film of the present invention can use the front side of the base for As the light incident surface, it is suitable for solar cells.

Hereinafter, the structure in which the a-Si film (α) and the a-Si film (β) are arranged on the base 101 is referred to as an intermediate structure 1A ( 1 ). The structure in which the first transparent conductive film 104 and the second transparent conductive film 114 are arranged on the intermediate structure 1A( 1 ) is a substrate with a transparent conductive film 10A( 10 ).

In addition, the solar cell 100A ( 100 ) is a structure in which an electrode 105 and an electrode 115 are arranged on the substrate 10A ( 10 ) with a transparent conductive film using a crystalline silicon substrate as the substrate 101 .

Regarding the substrate 10A ( 10 ) with a transparent conductive film having the above-mentioned structure ( FIG. 5 ), that is, having the first transparent conductive film 104 and the second transparent conductive film 114 and produced by the production equipment and production method of the present invention, which will be described in detail later, In other words, from Table 2 described later, it was confirmed that the transparent conductive film-attached substrate 10A ( 10 ) has a structure in which transparent conductive films having different hydrogen contents are arranged on the front side and the back side of the base. Since the substrate with a transparent conductive film having this structure can use the front side of the base as a light incident surface, it is suitable for use in solar cells.

In addition, the use of the solar cell with the transparent conductive film substrate having the above-mentioned structure can improve the fill factor (F.F.: Fill Factor) and the power generation efficiency (Eff).

In addition, although not clearly shown in FIG. 5 , an anti-reflection layer (Anti Reflection layer: AR layer) may be provided on the front surface 101 a side of the base body 101 as needed. As the antireflection layer, for example, an insulating nitride film, a silicon nitride film, a titanium oxide film, an aluminum oxide film, or the like is suitably used.

6 and 7 are flowcharts showing a method of manufacturing a substrate with a transparent conductive film, FIG. 6 shows a conventional example, and FIG. 7 shows an embodiment of the present invention. The embodiment of the present invention is different from the conventional example in the steps of "S16 and S17" described in detail below.

The conventional substrate with a transparent conductive film is formed through the process flow of S51 to S58 shown in FIG. 6 . That is, by performing the steps of "preparing c-Si(n), forming texture (both sides), forming i-type a-Si (both sides), forming p-type a-Si (front side), forming n-type a-Si (back side)," ), forming anhydrous TCO (front side), forming anhydrous (or anhydrous) TCO (back side) and forming electrodes (both sides)” composition of eight process processing and manufacturing.

In particular, in the conventional manufacturing method of a substrate with a transparent conductive film, a "process gas without water" is used when forming a TCO film on the front side as a light-receiving surface, and a "process gas without water" is used when forming a TCO film on the back side that is a non-light-receiving surface. When the film is formed in this order, the "water-containing process gas" used to form the back side TCO film will flow into the front side TCO film surface that has been previously formed into a film, and when water adheres Electrodes are formed on the surface of the TCO film in the state of Therefore, electrical failure may occur between the front-side TCO and the electrodes.

In contrast, the substrate with a transparent conductive film of the present invention is formed through the process flow of S11 to S18 shown in FIG. 7 . That is, by performing "preparation of c-Si(n), formation of texture (both sides), formation of i-type a-Si (both sides), formation of p-type a-Si (front side), formation of n-type a-Si (back side)" in this order , formed with water TCO (front side), formed with anhydrous TCO (back side) and formed electrodes (both sides)" composed of eight processes to manufacture. When the film is formed in this order, since the "non-water-free process gas" is used for the TCO film on the back side, even if the non-water process gas flows into the front-side TCO film surface where the film has been formed beforehand, it is impossible to It was in the state where water adhered to the front side TCO film surface. This makes it possible to form electrodes on the front side TCO film surface without being affected by water. Therefore, the problem that electrical failure occurs between the front-side TCO and the electrode is solved.

In order to manufacture the said board|substrate with a transparent conductive film of this invention, the manufacturing equipment of the board|substrate with a transparent conductive film as shown in FIG. 1 is suitably used, for example. FIG. 2 is a cross-sectional view showing an example of a base body in a state in which it is placed on a tray in the manufacturing facility of FIG. 1 . Hereinafter, the manufacturing facility of the substrate with a transparent conductive film of the present invention will be described in detail with reference to FIGS. 1 and 2 .

<Sputtering Equipment>

In the method for producing a substrate with a transparent conductive film of the present invention, the a-Si film (α, β) corresponding to the base of the transparent conductive film is used as a film previously formed on the substrate 101 by a known CVD apparatus. Here, the two transparent conductive films 104 ( TCO1 ) and 114 ( TCO2 ) can be formed by a manufacturing facility (hereinafter, referred to as a sputtering facility) that performs film formation using a sputtering method as shown in FIG. 1 . The manufacturing facility 700 is an in-line sputtering facility, and is a horizontal conveyance type sputtering facility provided with a conveyance mechanism that holds and conveys the substrate 101 horizontally. The discharge form of the sputtering apparatus 700 is not limited to DC, and may be RF or superposition of (DC+RF).

In the sputtering apparatus shown in FIG. 1, a plurality of process chambers [a loading chamber L, a heating chamber H, a film formation inlet chamber ENT, a first film formation chamber SP1, a second film formation chamber SP2, a first film formation chamber SP1, a second film formation chamber SP2, a second film formation chamber The third film formation chamber SP3, the fourth film formation chamber SP4, the film formation outlet chamber EXT, the transport chamber B, and the take-out chamber UL]. The tray 400 carrying the substrate 101 [intermediate structure 1A(1)] on which the a-Si film (α, β) is formed passes through the respective process chambers in order, thereby fabricating the intermediate structure 1A(1) Implementation of the present invention transparent conductive film.

That is, as will be described later, in the present invention, the substrate 101 heat-treated at a desired temperature passes through the four film forming chambers ( SP1 → SP2 → SP3 → SP4 ), so that the front side of the substrate 101 [serving as a light incident surface On the a-Si film (α) of the substrate 101], “the first transparent conductive film 104 (TCO1) with a large hydrogen content” is formed on the back side of the substrate 101 [on the a-Si film (β) serving as a non-light incident surface] A second transparent conductive film 114 (TCO2) having a small hydrogen content is formed.

When the first transparent conductive film 104 (TCO1) and the second transparent conductive film 114 (TCO2) are formed by sputtering, the tray 400 having the structure shown in FIG. 2 is suitably used. That is, the tray 400 is constituted by a main body 401 having a base for exposing the object to be processed, a first protruding portion 402 located inside the main body 401 , and second protruding portions 403 a and 403 b located outside the main body 401 . The first opening 400a and the second opening 400b of the front α and the rear β of the 101 .

The first protrusion 402 mounts the base 101 inside the main body 401 so that the first opening 400a is set larger than the second opening 400b. Accordingly, the first opening portion 400 a is defined by the inner side surface 401 s of the main body 401 , and the second opening portion 400 b is defined by the inner side surface 402 s of the protruding portion 402 . This is to form the first transparent conductive film 104 (TCO1) on the light incident side to have a larger area than the second transparent conductive film 114 (TCO2) on the non-light incident side.

The outside of the main body 401 is provided with second protrusions 403a and 403b. In the traveling direction (arrow direction in FIG. 2 ) of the tray (also referred to as a specific tray) 400 , the second protrusions 403 a extending in the direction of the front tray (also referred to as an advance tray) 410 and toward the rear tray ( The second protrusion 403b extending in the direction of the rear tray (also referred to as the rear tray) 420 is provided so that the connection position with the main body 401 is vertically reversed. That is, the second protrusion 413b is arranged on the front tray 410 so as to overlap with the second protrusion 403a of the tray 400 . Similarly, the rear tray 420 is provided with a second protrusion 423a so as to overlap with the second protrusion 403b of the tray 400 .

Thereby, the second protrusions 403a of the tray 400 and the second protrusions 413b of the front tray 410 are kept in the overlapping state, and the second protrusions 403b of the tray 400 and the second protrusions 423a of the rear tray 420 are maintained in the overlapping state. At the same time, the three trays 400, 410, and 420 are connected to perform sputtering film formation of the first transparent conductive film 104 (TCO1) and the second transparent conductive film 114 (TCO2).

In the manufacturing facility of the present invention, the trays 400 , 410 , and 420 on which the base body 101 is placed are connected in the advancing direction of the trays, and there is no space between the trays. Therefore, the possibility that the sputtered particles reach the non-film-forming surface of the substrate 101 (for example, when the front surface is the film-forming surface, the back surface is the non-film-forming surface) through the gaps between the trays can be greatly reduced. Likewise, the entrainment of the process gas for sputtering can also be suppressed.

Therefore, the present invention realizes a manufacturing apparatus for a substrate with a transparent conductive film, which can prevent sputtering particles from adhering to the non-film-forming surface of the substrate 101 or the non-film-forming surface of the substrate 101 being exposed to the process gas for sputtering adverse conditions in . This effect is extremely effective in the present invention in which the substrate 101 heat-treated at a desired temperature passes through the four film-forming chambers ( SP1 → SP2 → SP3 → SP4 ) so that the substrate 101 is formed on the front side of the substrate 101 . [On the a-Si film (α) serving as the light incident surface] A first transparent conductive film 104 (TCO1) with a large hydrogen content is formed, on the back side of the substrate 101 [a-Si film serving as a non-light incident surface ( β)] A second transparent conductive film 114 (TCO2) with a small hydrogen content is formed.

In the sputtering apparatus of FIG. 1, a plurality of process chambers [a loading chamber L, a heating chamber H, a film formation inlet chamber ENT, a first film formation chamber SP1, a second film formation chamber SP2, and a third film formation chamber are arranged in series. The chamber SP3, the fourth film formation chamber SP4, the film formation outlet chamber EXT, the transport chamber B, and the take-out chamber UL]. The sputtering apparatus of FIG. 1 includes a mechanism (not shown) for carrying the substrate 101 [intermediate structure 1A( 1 )] and holding the substrate 101 horizontally from the loading chamber L to the extraction chamber UL.

In the sputtering apparatus of FIG. 1 , reference numerals DV1 to DV6 all denote gate valves.

The first gate valve DV1 blocks between the air space outside the apparatus and the inner space of the loading chamber L.

The second gate valve DV2 blocks the space between the inner space of the loading chamber L and the inner space of the heating chamber H.

The third gate valve DV3 blocks the space between the inner space of the heating chamber H and the inner space of the film formation inlet chamber ENT. The fourth gate valve DV4 blocks the space between the inner space of the film formation outlet chamber EXT and the inner space of the transfer chamber B. The fifth gate valve DV5 blocks the space between the inner space of the transport chamber B and the inner space of the extraction chamber UL. The sixth gate valve DV6 blocks the space between the inner space of the extraction chamber UL and the atmospheric space outside the apparatus.

In the sputtering apparatus of FIG. 1, six chambers (film formation inlet chamber ENT, first film formation chamber SP1, second film formation chamber SP2, third film formation chamber SP3, fourth film formation chamber SP4 and film formation All the inner spaces of the outlet chamber EXT) are connected to form a vacuum chamber. Among the six chambers, the "dotted line" indicating the partition of the chambers located at the adjacent positions from each other means that the inner spaces of the chambers located at the adjacent positions are communicated with each other.

Both the front surface and the back surface of the substrate 101 [intermediate structure 1A( 1 )] placed on the tray 400 and carried into the inner space of the loading chamber L from the outer space of the sputtering facility are subjected to a known CVD method. The device is pre-formed with an a-Si film. The base body 101 can move only in the forward direction from the loading chamber L toward the extraction chamber UL in a state mounted on the tray 400 . That is, in the manufacturing facility shown in FIG. 1, the base body 101 mounted on the tray 400 does not need to be returned in the reverse direction [direction from the extraction chamber UL to the loading chamber L]. Therefore, the sputtering apparatus of FIG. 1 is excellent in mass productivity.

By performing the opening and closing operation of the first gate valve DV1, the substrate 101 is carried into the inner space of the loading chamber L from the air space (outside the sputtering apparatus). Using the first exhaust device P11, the inner space of the loading chamber L is set to a desired reduced pressure atmosphere. In the loading chamber L, heat treatment is performed from both surfaces of the base body 101 using the temperature adjusting devices H11 and H12 of the loading chamber L as necessary. By performing the opening and closing operation of the second gate valve DV2, the substrate 101 that has not been heat-treated or the substrate 101 that has been heated to a desired temperature moves from the loading chamber L to the heating chamber H.

Next, with respect to the base body 101 moved from the loading chamber L into the heating chamber H, at the point A, heat treatment is performed from both sides of the base body 101 by the temperature adjustment devices H21 and H22. At this time, a desired decompressed atmosphere is maintained in the inner space of the heating chamber H using the second exhaust device P21. By performing the opening and closing operation of the third gate valve DV3, the substrate 101 having a desired temperature in the heating chamber H moves from the heating chamber H to the film formation inlet chamber ENT.

Next, with respect to the base body 101 moved from the heating chamber H to the film formation inlet chamber ENT, at the point B, heat treatment is performed from both sides of the base body 101 by the temperature adjustment devices H311 and H312. The substrate 101 having a desired temperature in the film formation inlet chamber ENT passes through the inner spaces of the four film formation chambers ( SP1 → SP2 → SP3 → SP4 ) from the film formation inlet chamber ENT to perform desired film formation, and then moves to the film formation outlet Room ext.

The first transparent conductive film 104 ( TCO1 ) and the second transparent conductive film 104 ( TCO1 ) and the second transparent conductive film are formed in cooperation with the first film formation chamber SP1 , the second film formation chamber SP2 , the third film formation chamber SP3 and the fourth film formation chamber SP4 located in the latter stage. The atmosphere of the film-forming inlet chamber ENT in which the substrate 101 is accommodated is adjusted according to the atmospheric conditions (sputtering film-forming conditions, etc.) at the time of the film 114 (TCO 2 ). The first transparent conductive film 104 ( TCO1 ) and the second transparent conductive film 114 ( TCO2 ) will be formed on the front and back of the base 101 .

In the first film-forming chamber SP1 located after the film-forming inlet chamber ENT, a temperature adjusting device H322 is disposed, and the temperature adjusting device H322 heats the back surface of the base body 101 when the base body 101 passes through the point C. Thereby, the temperature of the substrate 101 immediately before the formation of the first transparent conductive film 104 ( TCO1 ) in the next second film formation chamber SP2 can be adjusted.

In the second film forming chamber SP2 located after the first film forming chamber SP1 are arranged: a temperature adjusting device H332 for heat-treating the back surface of the base body 101 when the base body 101 passes through the point D; and a first film forming device for The structure of a pair of rotating targets TG21 and TG22 of the first transparent conductive film 104 ( TCO1 ) is formed on the front side of the base body 101 . As a result, the film-forming temperature of the substrate 101 when the first transparent conductive film 104 ( TCO1 ) is formed can be adjusted from the back surface (the lower surface in FIG. 1 ) that is the non-film-forming surface. With respect to the pair of rotating targets TG21 and TG22, the lead-out ports of the two process gas supply mechanisms G21 and G22 are arranged at the left position in the traveling direction of the base body 101.

The substrate 101 whose temperature has been adjusted in this way passes through the point D of the second film forming chamber SP2. At this time, the tray 400 horizontally maintains the base body 101 such that the front surface of the base body 101 faces the first targets TG21 and TG22. The base 101 passes through the point D through the tray 400 , and the first transparent conductive film 104 ( TCO1 ) is formed only on the front side of the base 101 by, for example, DC sputtering using the first targets TG21 and TG22 . Thereby, the first transparent conductive film 104 ( TCO1 ) is formed on the a-Si film (α) on the front surface ( 101 a ) side of the base body 101 . Furthermore, as described above, the discharge form of the sputtering method in the present invention is not limited to DC, and may be RF or superposition of (DC+RF).

At this time, an inert gas (eg, Ar) G21 and a reactive gas (eg, O ₂ gas) or a hydrogen-containing gas (eg, H ₂ O) G22 are supplied so as to be sprayed toward the left target TG21 in the traveling direction of the substrate as the first process gas for forming plasma. In the second film formation chamber SP2, the first targets TG21 and TG22 are arranged above the base body 101, and the sputtering of the down deposition method is performed.

3 is an enlarged cross-sectional view showing a gas lead-out portion in a configuration example having two targets. The pair of targets shown in FIG. 3 represents a pair of first targets TG21 and TG22 arranged in the second film formation chamber SP2 of FIG. 1 . In FIG. 3 , reference numeral 400 denotes a tray on which the base body is mounted, and a thick white hollow arrow (toward the right side of the drawing) indicates the moving direction of the tray (ie, the base body).

As shown in FIG. 3 , it is preferable to have a configuration in which the first film formation apparatus is constructed in the film formation chamber and the vicinity of the first targets TG21 and TG22 for forming the first transparent conductive film on the front side of the base body , the gas outlet (arrow) of the first process gas introduction mechanism for supplying the reactive gas in the first process gas or the hydrogen-containing gas G22 in the direction of movement of the substrate [(in FIG. 3 from the right end of the tray 400 It is arrange|positioned at the position where the 1st process gas G22 is injected toward the target TG21 located on the left among the 1st targets TG21 and TG22 in the direction of the thick white arrow extending to the right. According to this configuration, hydrogen can be consumed by the cathode on the left, and film formation with a small amount of hydrogen can be performed by the cathode on the right. As a result, the first transparent conductive film formed on the front surface side of the substrate can be a film in which the hydrogen concentration of the initial growth portion is high and the hydrogen concentration decreases as the film thickness increases.

3, the gas outlet of the first process gas introduction means for supplying the inert gas G21 in the first process gas is omitted, but it is not necessarily arranged on the left side like the reactive gas or the hydrogen-containing gas G22. For example, it may be arranged on the right side or the like.

In addition, instead of the above-mentioned structure (the structure in which the first process gas G22 is sprayed toward the target TG21 ), a structure may be adopted in which the first process gas G22 containing the hydrogen is supplied in the film formation chamber. A gas lead-out portion of a process gas introduction mechanism is disposed at a position where the first process gas G22 is ejected toward a discharge space (plasma) generated in the first film forming apparatus that constitutes the The front side of the base is formed between the first targets TG21 and TG22 of the first transparent conductive film and the moving base. As a result, a state in which hydrogen is uniformly contained in the discharge space (plasma) can be achieved, so that the first transparent conductive film formed on the substrate can achieve a uniform hydrogen content in the film.

In the structure of FIG. 3 , that is, the structure in which the first target is formed of two cylindrical targets TG21 and TG22, the arrangement of the flue is very effective. When the flue is arranged in the structure of FIG. 3 , it is preferable to set the flue C21 and C22 so as to surround the two first targets TG21 and TG22. By providing the flue, it is possible to suppress the formation of a film (second transparent conductive film) on the back side of the substrate by the hydrogen-containing first process gas 22 used to form the first transparent conductive film on the front side of the substrate. formation).

4 is an enlarged cross-sectional view showing a gas lead-out portion in a configuration example having three targets.

In FIG. 3, although the structure in which the 1st target TG21, TG22 is a pair is shown, this invention is not limited to this. For example, as shown in FIG. 4 , the first target is formed of three cylindrical targets TG21, TG22, and TG23, and in the moving direction of the substrate [(extending from the right end of the tray 400 toward the right in FIG. 4) white hollow TG23, TG21, TG22 are arranged in order from left to right in the direction of the thick arrow], and the present invention can also be applied to this structure. TG21 and TG22 in FIG. 4 are the same pair of first targets as in FIG. 3 .

In the moving direction of the substrate, when the first first target TG23 is located in the front section alone, and the second and third first targets TG21 and TG22 form a pair and are located in the rear section, only the first target TG21 and TG22 are located in the rear section. What is necessary is just to arrange|position the gas lead-out part of the 1st process gas introduction means which supplies a 1st process gas to the 1st target TG23. At this time, the gas lead-out portion of the first process gas introduction mechanism for supplying the first process gas to the first target TG23 is not limited to the left side in the moving direction of the substrate, and may be arranged, for example, on the right side.

Since the first process gas supplied to the first target TG23 located in the front stage flows in the direction of the first targets TG21 and TG22 in the rear stage, it can also be supplied to the first targets TG21 and TG22 in the rear stage. Therefore, the gas lead-out portion (the gas lead-out portion shown in FIG. 3 ) of the first process gas introduction mechanism for supplying the first process gas to the first targets TG21 and TG22 in the subsequent stage is not necessarily arranged in the configuration shown in FIG. 4 . middle.

It is also effective to provide a flue in the structure of FIG. 4 , that is, the structure in which the first target is formed of three cylindrical targets TG21, TG22, and TG23. When the flue is arranged in the structure of FIG. 4 , it is preferable to provide the first flues C23 and C24 so as to surround the first first target TG23 and to surround the second and third first targets TG21 and C24. The second flue C21 and C22 are set in the way of TG22. As a result, in the structure of FIG. 4 , similarly to the structure of FIG. 3 described above, the effect of providing the flue is stably obtained [that is, the use of the The effect of the influence of the hydrogen-containing first process gas G22 on the film formation (formation of the second transparent conductive film) on the back surface side of the substrate].

In addition, the first target may be constructed of four or more cylindrical targets. When the number of the first targets is four, the arrangement of the above-mentioned pair of targets may be repeated twice.

Similarly, when there are five first targets, the arrangement of one first target and a pair of targets may be repeated twice. That is, the present invention can be applied not only to the case where the first target is formed of an even-numbered cylindrical target, but also to a case where the first target is formed of an odd-numbered cylindrical target.

In the third film-forming chamber SP3 located after the second film-forming chamber SP2, a temperature adjusting device H331 for heat-treating the front surface of the base body 101 when the base body 101 passes through the point E is disposed.

In the fourth film-forming chamber SP4 located after the third film-forming chamber SP3 are arranged: a temperature adjusting device H341 for heat-treating the front surface of the substrate 101 when the substrate 101 passes through the point F; and a second film-forming device for using A pair of rotating targets TG41 and TG43 on which the second transparent conductive film 114 (TCO2) is formed on the back surface side of the base body 101 are formed. Thereby, the film-forming temperature of the substrate 101 when the second transparent conductive film 114 (TCO 2 ) is formed can be adjusted from the front surface (the upper surface in FIG. 1 ), which is the non-film-forming surface. For the two pairs of rotating targets TG41 and TG42, the lead-out ports of the two process gas supply mechanisms G41 and G42 are arranged at the left positions in the traveling direction of the base body 101.

The substrate 101 whose temperature has been adjusted in this way passes through the point F of the fourth film-forming chamber SP4. At this time, the tray 400 horizontally maintains the base body 101 so that the back surface of the base body 101 faces the second handles TG41 and TG42. The base 101 passes through the point F through the tray 400, and the second transparent conductive film 114 (TCO2) is formed only on the back side of the base 101 by, for example, DC sputtering using the second targets TG41 and TG42. As a result, the second transparent conductive film 114 ( TCO 2 ) is formed on the a-Si film (β) on the back surface ( 101 b ) side of the base body 101 . In addition, as described above, the discharge form of the sputtering method in the present invention is not limited to DC, and may be RF or superposition of (DC+RF).

At this time, an inert gas (for example, Ar gas) or a reactive gas (for example, O ₂ gas) G42 is supplied as a plasma forming agent in such a manner as to be sprayed toward the left target TG41 or the right target TG42 in the traveling direction of the substrate. process gas. In the fourth film formation chamber SP4, the targets TG41 and TG42 are arranged below the base body 101, and sputtering for upward deposition is performed.

In other words, in the film-forming chamber, in the vicinity of the second targets TG41 and TG42, which configure the second film-forming apparatus and form the second transparent conductive film on the back side of the substrate, a second target TG41 and TG42 for supplying no hydrogen is disposed. The gas outlet of the second process gas introduction mechanism of the second process gas.

For example, a suitable configuration of the gas lead-out portion of the second process gas introduction mechanism is as follows: that is, the gas lead-out portion is arranged on the left side of the second targets TG41 and TG42 in the moving direction of the substrate. The target TG41 or the target TG42 on the right side is at the position where the second process gas is injected, but the present invention is not limited to this structure.

The second target is also not limited to the above-described pair of structures. Like the aforementioned first target, three cylindrical targets may be arranged in a row as the second target, or four or more cylindrical targets may be arranged in series as the second target. That is, the present invention is applied not only to the case where the second target is formed of even-numbered cylindrical targets, but also to the case where the second target is formed of odd-numbered cylindrical targets.

FIG. 1 discloses a manufacturing facility of a standard configuration in which film formation is not performed in the first film formation chamber SP1 and the third film formation chamber SP3, but the present invention is not limited to this configuration. For example, the same film formation apparatus as that of the second film formation chamber SP2 may be installed in the first film formation chamber SP1. The same film forming apparatus as that of the fourth film forming chamber SP4 may be installed in the third film forming chamber SP3.

For the sputtering apparatus of FIG. 1, there are six chambers (film formation inlet chamber ENT, first film formation chamber SP1, second film formation chamber SP2, third film formation chamber SP3, fourth film formation chamber SP4 and In the film formation outlet chamber EXT), a plurality of exhaust devices (P31, P332, P331, and P352) are arranged in order to make the communicating internal space a decompressed atmosphere. That is, a gate valve, a gate valve, a differential pressure valve, etc. are not provided at all between the six chambers, for example, between adjacent film-forming chambers. Thereby, the above-mentioned "structure in which a plurality of trays (for example, trays 400, 410, and 420) are connected and moved in the traveling direction" can be realized.

The third exhaust device P31 is connected to a position that mainly exhausts the inner space of the film formation inlet chamber ENT. The fourth exhaust device P332 is connected to a position that mainly exhausts the inner space of the second film formation chamber SP2. The fifth exhaust device P331 is connected to a position that mainly exhausts the inner space of the third film formation chamber SP3. The sixth exhaust device P352 is connected to a position that mainly exhausts the inner space of the film formation outlet chamber EXT.

More important of these are the fourth exhaust device P332 and the fifth exhaust device P331. The fourth evacuation device P332 mainly evacuates the inner space of the second film formation chamber SP2 in which the film formation device composed of the pair of rotating targets TG11 and TG22 for forming the first film formation chamber is disposed. Transparent conductive film 104 (TCO1). The fifth exhaust device P331 mainly exhausts the inner space of the third film formation chamber SP3 located in front of the inner space of the fourth film formation chamber SP4 in which the two pairs of rotating targets TG41 are arranged. , TG42 constituted film forming apparatus, the rotating target TG41, TG42 is used to form the second transparent conductive film 114 (TCO2).

Thereby, the fourth exhaust device P332 and the fifth exhaust device P331 function as the process gas introduced from the two process gas supply devices G21 and G22 for forming the first transparent conductive film 104 (TCO1) [Gas for forming the first transparent conductive film 104 (TCO1) with a high hydrogen content] does not affect the film formation of the second transparent conductive film 114 (TCO2) with a small hydrogen content in a subsequent process.

The method of assisting the function so as not to affect the film formation of the second transparent conductive film 114 (TCO 2 ) with a low hydrogen content in the subsequent process is the above-mentioned “the first step is performed by connecting the three trays 400 , 410 , and 420 ”. Structure of sputtering film formation of a transparent conductive film 104 (TCO1) and a second transparent conductive film 114 (TCO2).

In the manufacturing apparatus of the present invention, a plurality of trays (eg, trays 400, 410, 420) are connected and moved in the traveling direction, so that there is no gap between the trays, and the gap between the trays for sputtering particles can be greatly reduced On the other hand, the possibility of reaching the non-film-forming surface of the substrate 101 (for example, when the front surface is the film-forming surface, the back surface is the non-film-forming surface). Likewise, the entrainment of the process gas for sputtering can be suppressed. Therefore, according to the present invention, it is possible to stably form the second transparent conductive film 114 (TCO2), which is produced after the first transparent conductive film 104 (TCO1) is formed and has a small hydrogen content. membrane.

In this way, through the four film forming chambers (SP1→SP2→SP3→SP4), the following substrate 101 can be obtained: that is, the front side of the substrate 101 [on the a-Si film (α) serving as the light incident surface] "The first transparent conductive film 104 (TCO1) with a large hydrogen content" is formed, and on the back side of the base 101 [on the a-Si film (β) serving as a non-light incident surface], a second transparent conductive film 104 with a small hydrogen content is formed. Transparent conductive film 114 (TCO2). The substrate 101 passing through the inside of the four film formation chambers ( SP1 → SP2 → SP3 → SP4 ) is moved to a point G located in the inner space of the film formation outlet chamber EXT by the tray 400 .

After the substrate 101 on which the first transparent conductive film 104 (TCO1) and the second transparent conductive film 114 (TCO2) are formed is moved to the film formation outlet chamber EXT (point G), the opening and closing operation of the fourth gate valve DV4 is performed, and the substrate 101 It moves from the film formation outlet chamber EXT to the transfer chamber B.

After the base body 101 has moved to the transport chamber B (site H), the opening and closing operation of the fifth gate valve DV5 is performed, and the base body 101 is moved from the transport chamber B to the extraction chamber UL (site I). Then, after the pressure inside the extraction chamber UL is set to atmospheric pressure, the opening and closing operation of the sixth gate valve DV6 is performed, thereby forming a substrate on which the first transparent conductive film 104 ( TCO1 ) and the second transparent conductive film 114 ( TCO2 ) are formed 101 is carried out to the outside of the sputtering apparatus.

As described above, in the sputtering apparatus of FIG. 1 , in order to prevent the hydrogen-containing gas introduced into the inner space of the second film formation chamber SP2 located in the front stage from flowing out to the inner space of the fourth film formation chamber located in the rear stage, the The configuration in which the fourth exhaust device P332 and the fifth exhaust device P331 are provided to the pair of rotating targets TG11 and TG22 for forming the first transparent conductive film 104 ( TCO1 ) is presented.

In addition, in the sputtering apparatus of FIG. 1 , in order to prevent the hydrogen-containing gas introduced into the inner space of the second film formation chamber SP2 located in the front stage from flowing out to the inner space of the fourth film formation chamber located in the rear stage, the The tray 400 that moves in the state where the base body 101 is placed is also designed. That is, the trays 400 , 410 , and 420 for placing the base 101 are connected in the advancing direction of the trays, and the trays 400 , 410 , and 420 are connected so as to be movable without a gap between the trays.

The present invention realizes a sputtering apparatus capable of largely suppressing the flow of the process gas for sputtering from one side of the substrate to the other side (eg, from the front side to the back side) through the design of the exhaust device and the tray.

In addition, since the sputtering apparatus of FIG. 1 is an in-line sputtering apparatus, there are advantages that the substrate with a transparent conductive film (and the solar cell) can be manufactured with high productivity and the occupied space of the apparatus can be reduced. Furthermore, in the case of an in-line sputtering apparatus, it is suitable to manufacture a uniform film under the same film-forming conditions.

On the other hand, in the case of using a general single-wafer type (single-leaf type) manufacturing equipment, it is necessary to take out the previously formed substrate (substrate after film formation) from the film formation chamber to the moving chamber every time one substrate is processed. (transfer chamber), and the substrate to be film-formed next (pre-film-forming substrate) is transported from the moving chamber into the film-forming chamber. In addition, after taking out the substrate after film formation, it is necessary to clean the film formation chamber by removing residual gas in the film formation chamber, and then transport the pre-film formation substrate into the film formation chamber. However, in this case, since the residual components of the residual gas adhere to the walls of the film formation chamber, etc., the residual components cannot be completely removed from the film formation chamber, and there is a possibility that the residual components may affect the characteristics of the film to be formed later. . In addition, when the film is formed on the substrate, the operation of introducing the process gas and the operation of stopping the introduction of the process gas are performed in the film formation chamber, and the ON/OFF of the discharge is performed. In this case, it is necessary to control the amount of water adsorbed on the base film every time one substrate is processed, which tends to cause difficulty in the process.

On the other hand, in the case of using the in-line sputtering apparatus, the substrate 101 moves only in the forward direction from the loading chamber L toward the taking-out chamber UL, and passes through the communicating inner space, so that the a- The first transparent conductive film 104 (TCO1) and the second transparent conductive film 114 (TCO2) are formed on the Si films (α, β), respectively, so that the amount of water adsorbed on the a-Si film serving as the base film can be easily controlled. . In addition, since the power supply is always turned on (ON), the time that contributes to the film formation is 100[%], and high productivity and low running cost can be realized at the same time.

In addition, in the sputtering apparatus of FIG. 1 , the a-Si films (α, β) on both sides of the substrate 101 are respectively formed into films in the film forming chambers ( SP1 , SP2 , SP3 , SP4 ) having continuous closed spaces. The first transparent conductive film 104 (TCO1) and the second transparent conductive film 114 (TCO2), so the substrate 101 will not be exposed to the atmosphere, and the a-Si film ( α, β) respectively form the first transparent conductive film 104 (TCO1) and the second transparent conductive film 114 (TCO2) (film formation on the front and back is performed in a consistent vacuum state).

Next, a plurality of process chambers [loading chamber L, heating chamber H, film formation inlet chamber ENT, first film formation chamber SP1, second film formation chamber SP2, third film formation chamber The tray temperatures in SP3, the fourth film formation chamber SP4, the film formation outlet chamber EXT, the conveyance chamber B, and the take-out chamber UL] are verified, and the verification results will be described.

Fig. 8 is a table showing the tray temperatures [°C] in Experimental Examples 1 to 4. In Fig. 8, "Pos." is the name of the process room, and "Time" is the time since the tray started to move. For example, "240" means "after 240 seconds from when the tray starts to move". The numbers described in the columns of Experimental Examples 1 to 4 are the temperatures [° C.] of the trays at the time (“time”) (after heat treatment by the temperature control device arranged in each process chamber).

FIG. 9 is a graph showing the tray temperature [° C.] in FIG. 8 . In FIG. 9 , the solid line represents the experimental example 1, the short dashed line represents the experimental example 2, the long dashed line represents the experimental example 3, and the dashed-dotted line represents the experimental example 4.

<Experimental example 1>

Under the set conditions of Experimental Example 1, by gradually increasing the temperature in the charging chamber L and the heating chamber H, the four film-forming chambers (SP1 to SP4, especially SP3, SP4) had temperature peaks. Therefore, the amount of water released from the surface of the tray to the inner space of the film formation chamber increases, which may adversely affect the process gas during sputtering.

<Experimental example 2>

Under the set conditions of Experimental Example 2, it was made to have a temperature peak by heating in the loading chamber L, and dewatered from the surface of the tray. In the process chamber located at a later stage than the loading chamber L, the tray temperature decreases monotonically. Thereby, a lower temperature state can be formed in the four film forming chambers ( SP1 to SP4 ) than when there is a temperature peak, so that the release or take-in of water can be reduced.

<Experimental example 3>

Under the set conditions of Experimental Example 3, sufficient dehydration was obtained from the tray surface by heating in the loading chamber L and the heating chamber H. Then, by setting the high temperature holding time also in the film formation inlet chamber ENT and the four film formation chambers ( SP1 to SP4 ), the degassing effect is enhanced.

<Experimental example 4>

Under the set conditions of Experimental Example 4, the loading chamber L was only evacuated, and dehydration from the tray surface was performed by heating in the heating chamber H. Then, as in Experimental Example 3, the degassing effect was enhanced by setting the high temperature holding time also in the film formation inlet chamber ENT and the four film formation chambers (SP1 to SP4). Although the temperature is slightly increased by the temperature adjustment at the time of back surface film formation, the effect on the exhaust gas is slight because heating and degassing can be performed in advance.

FIG. 10 is a graph showing the hydrogen content distribution of the transparent conductive film (in the case of H ₂ O/Ar=0%). FIG. 11 is a graph showing the hydrogen content distribution of the transparent conductive film (in the case of H ₂ O/Ar=6%). 10 and 11 show the results obtained by SIMS analysis. The measuring instrument used for the SIMS analysis was SIMS6650 manufactured by Alpha Corp. As measurement conditions, the primary ion species was Cs ⁺ , and the accelerating voltage was 5 kV.

In FIGS. 10 and 11 , the horizontal axis represents the depth of the transparent conductive film (time to excavate the transparent conductive film from the front surface to the back surface of the transparent conductive film), the vertical axis on the left represents the hydrogen content [atoms/cm ³ ], and the vertical axis on the right represents the hydrogen content [atoms/cm 3 ]. The vertical axis represents the secondary ion intensity (16O, 115In, 28Si).

The following points are clarified from FIG. 10 and FIG. 11 .

The transparent conductive film of FIG. 10 corresponds to the second transparent conductive film 114 (TCO 2 ) described above, and its hydrogen content is on the order of 10 ²⁰ [atoms/cm ³ ].

The transparent conductive film of FIG. 11 corresponds to the first transparent conductive film 104 (TCO1) described above, and the hydrogen content thereof is on the order of 10 ²¹ [atoms/cm ³ ].

Table 1 shows typical film-forming conditions when forming the first transparent conductive film 104 (TCO1) and the second transparent conductive film 114 (TCO2). In the item column of Table 1, "Front" means the first transparent conductive film 104 (TCO1) formed on the front side of the base, and "Rear" means the second transparent film 104 (TCO1) formed on the back side of the base Transparent conductive film 114 (TCO2).

[Table 1]

project forward back cathode rotate rotate Material In₂O₃ Department TCO In₂O₃ Department TCO power 4.5kW 4.3kW power density 4.1kW/m 3.9kW/m temperature 90 90 Film thickness 100 100 Voltage 250 240 pressure 0.7 0.7 Ar 250 250 O₂ 5 6 H₂O 3 0 water pressure 4.60E-02 1.60E-02 Intermediate pump 2100L/s×1 2100L/s×1 water introduction location Between TGs on the left - water inlet towards the left TG - Gas analyzer directly below the cathode none

From the above results, the substrate with a transparent conductive film of the present invention is a substrate with a transparent conductive film in which a first transparent conductive film and a second transparent conductive film are respectively arranged on the a-Si films arranged on the front and rear surfaces of the base body. , the substrate with a transparent conductive film may be formed such that the hydrogen content contained in the first transparent conductive film is defined as _CH1 [atomic number/cm ³ ], and the hydrogen contained in the second transparent conductive film When the content is defined as _CH2 [number of atoms/cm ³ ], the relational expression of _CH1 > _CH2 is satisfied. At this time, the C _H1 is in the order of 10 ²¹ , and the C _H2 [number of atoms/cm ³ ] is in the order of 10 ²⁰ .

The hydrogen content C _H1 [atoms/cm ³ ] contained in the first transparent conductive film was evaluated by changing the ratio of "water (H ₂ O)/Ar" under the conditions of "before" in Table 1, and the evaluation The results are shown in Table 2.

[Table 2]

H₂O/Ar[%] H₂ content [atomic number/cm³] 0 4.81E+20 0.3 2.15E+21 2 4.06E+21 6 7.03E+21

Four types of solar cells composed of the structures shown in FIG. 3 were fabricated. Four types of solar cells were provided as a transparent conductive film (Front side TCO) provided on the front side (light-receiving surface side) of the base body and a transparent conductive film [Rear side TCO (Rear side TCO) provided on the back side of the base body. TCO)] with different combinations of hydrogen content. Other than that, the structure is the same. Experimental Example 11 to Experimental Example 14 shown in Table 3 are four types of solar cells. As the evaluation results of the solar cells, the fill factor FF and the power generation efficiency Eff were evaluated.

[table 3]

Experimental example Front TCO rear TCO 11 There is water In₂O₃ system TCO Anhydrous In₂O₃ TCO 12 There is water In₂O₃ system TCO There is water In₂O₃ system TCO 13 Anhydrous In₂O₃ TCO Anhydrous In₂O₃ TCO 14 Anhydrous In₂O₃ TCO There is water In₂O₃ system TCO

When the fill factor FF is normalized by the numerical value of Experimental Example 14, it is 1.019 in the case of Experimental Example 11, 0.998 in the case of Experimental Example 12, and 1.007 in the case of Experimental Example 13.

When the power generation efficiency Eff is normalized by the numerical value of Experimental Example 14, it is 1.044 in the case of Experimental Example 11, 1.032 in the case of Experimental Example 12, and 1.010 in the case of Experimental Example 13.

As can be seen from the above results, when the front side of the substrate is set as the light incident surface, the hydrogen content contained in the first transparent conductive film is defined as CH1 [atomic number/cm ³ ], and the hydrogen content contained in the second transparent conductive film is defined as C _H1 [atoms/cm 3 ]. When the hydrogen content in the transparent conductive film is defined as _CH2 [atomic number/cm ³ ], the solar cell (Experimental Example 11) satisfying the relational expression of _CH1 > _CH2 can improve the fill factor (FF: Fill Factor) and Power Generation Efficiency (Eff). In addition, the fill factor is "the value obtained by dividing the maximum output power (Pmax) by the product of the open-circuit voltage (Voc) and the short-circuit current (Isc)", and the power generation efficiency is "the open-circuit voltage (Voc), the short-circuit current density (Jsc) and the Product of Fill Factor (FF)".

As mentioned above, although the invention made by the present inventors has been specifically described based on the embodiment, the present invention is not limited to the above-mentioned embodiment, and various modifications can of course be made without departing from the gist of the present invention.

Industrial Availability

The present invention can be widely used in manufacturing equipment with a transparent conductive film substrate, a manufacturing method with a transparent conductive film substrate, a substrate with a transparent conductive film, and a solar cell.

Description of reference numerals

L loading chamber

H heating chamber

ENT film formation inlet chamber

SP1 first film forming chamber

SP2 Second film formation chamber

SP3 third film forming chamber

SP4 fourth film forming chamber

EXT film formation outlet chamber

B delivery room

UL extraction chamber

DV1, DV2, DV3, DV4, DV5, DV6 gate valve

G21, G22 The first process gas introduction mechanism (the process gas supply device for the first transparent conductive film)

G41, G42 Second process gas introduction mechanism (process gas supply device for second transparent conductive film)

H11, H12, H21, H22, H311, H312, H322, H332, H331, H341 Thermostat

P11, P21, P31, P331, P332, P352, P41, P52 Exhaust

TG21, TG22 Rotary target for the first transparent conductive film (first film forming device)

TG41, TG42 Rotary target for second transparent conductive film (second film forming device)

α, β a-Si film

101 Matrix

104 The first transparent conductive film (TCO1)

114 Second transparent conductive film (TCO2)

400 trays

700 Sputtering Equipment

Claims (16)

1. a kind of manufacturing equipment with transparent conductive film substrate, including have third register and the first film formation device and second The film forming room of film formation device, the third register are heat-treated the matrix in the state of being placed in pallet, and described One film formation device and second film formation device are respectively formed the first transparent conductive film to the face side and back side of described matrix And second transparent conductive film, wherein

The film forming is indoor, construction first film formation device and forms the first electrically conducting transparent to the face side of described matrix Near first target of film, exist for supplying the gas leading-out portion of the first process gas introducing mechanism of the first hydrogeneous process gas It is disposed on the moving direction of described matrix and first process gas is sprayed to the target positioned at left side in first target On position,

The film forming is indoor, construction second film formation device and forms the second electrically conducting transparent to the back side of described matrix Near second target of film, it is equipped with the gas export for supplying the second process gas introducing mechanism of the second not hydrogeneous process gas Portion,

First target and second target configuration are in the film forming room, thus before described matrix is by first target When face, first transparent conductive film is formed by face side of the sputtering method to the matrix, and described in passing through in described matrix When before the second target, second transparent conductive film is formed by back side of the sputtering method to the matrix.

2. the manufacturing equipment according to claim 1 with transparent conductive film substrate, wherein

In the film forming room, it is configured in a manner of the inner space being connected between first target and second target The more than one exhaust apparatus for having air entry.

3. the manufacturing equipment according to claim 1 with transparent conductive film substrate, wherein

The pallet has the opening portion of the front and back for exposing described matrix and supports the position of the side of the matrix, In the film forming room, direction of travel arranged in a straight line arranging of multiple pallets along the pallet, and the spy in multiple pallets Determine pallet have when by before first target and second target on the direction of travel of the particular pallet be located at The position that the leading pallet of the front and back of the particular pallet and rear row pallet are overlapped respectively, from first target side or described When the particular pallet is observed in two target sides, the particular pallet and leading pallet and rear row support positioned at the front and back of the particular pallet Disk forms one group, and the manufacturing equipment has the side that particular pallet formation the same face is clipped with leading pallet and rear row pallet Formula controls the device of the movement of each pallet.

4. the manufacturing equipment according to claim 1 with transparent conductive film substrate, wherein

The film forming it is indoor, positioned at described matrix by the position before before first target and second target Inner space and be located across before each target and the inner space on the position that forms a film, each inner space configures There is the more than one third register.

5. the manufacturing equipment according to claim 1 with transparent conductive film substrate, wherein

In the film forming room, the gas of the first process gas introducing mechanism for supplying the first hydrogeneous process gas Leading-out portion is disposed on the position for spraying first process gas towards discharge space, and the discharge space generates described in the construction First film formation device and to the face side of described matrix formed the first transparent conductive film the first target and mobile described matrix it Between.

6. the manufacturing equipment according to claim 1 with transparent conductive film substrate, wherein

In the film forming room, it is equipped with flue in a manner of surrounding discharge space, the discharge space generates described in the construction First film formation device and to the face side of described matrix formed the first transparent conductive film the first target and mobile described matrix it Between.

7. the manufacturing equipment according to claim 5 with transparent conductive film substrate, wherein

In the film forming room, it is equipped with flue in a manner of surrounding discharge space, the discharge space generates described in the construction First film formation device and to the face side of described matrix formed the first transparent conductive film the first target and mobile described matrix it Between.

8. with the manufacturing equipment of transparent conductive film substrate described according to claim 1~any one of 7, wherein

Have loading room with the first register in the leading portion of the film forming room and with the heating room of the second register, First register in reduced atmosphere to from air atmosphere import and in be placed in pallet state and front and The matrix that the back side is equipped with a-Si is heat-treated, and second register is to the pallet and base come from loading room movement Body is heat-treated,

Have conveying room in the back segment of the film forming room and take out room, the conveying room is to the pallet come from film forming room movement It is cooled down with matrix, the room of taking out will export to atmosphere from reduced atmosphere from the conveying room mobile next pallet and matrix In atmosphere.

9. a kind of manufacturing method with transparent conductive film substrate,

Using at least having, the band according to any one of claims 8 for being packed into room, heating room, film forming room, conveying room and taking-up room is transparent to be led The manufacturing equipment of electrolemma substrate, it is described to form transparent conductive film on the Si film on the front and the back side for being disposed in matrix Matrix is placed on pallet,

The maximum value of the heat treatment temperature being fitted into room is being defined as T_L, by the heat treatment temperature in the heating room Maximum value is defined as T_H, the maximum value of the heat treatment temperature in the film forming room is defined as T_SPIn the case where, meet T_L≥T_SP、 Or T_H≥T_SPRelational expression, wherein the T_L, the T_HAnd the T_SPUnit be DEG C.

10. the manufacturing method according to claim 9 with transparent conductive film substrate, wherein

In the inner space of the inner space for being fitted into room and the heating room, by being arranged respectively at described matrix just The first register and the second register of surface side and back side is heat-treated described matrix.

11. the manufacturing method according to claim 9 with transparent conductive film substrate, wherein

The film forming it is indoor, positioned at described matrix by the position before before first target inner space and Pass through in the inner space on the position to form a film before first target positioned at the matrix, by configuring in the matrix The third register of non-film surface side is heat-treated the matrix.

12. the manufacturing method according to claim 9 with transparent conductive film substrate, wherein

The film forming it is indoor, positioned at described matrix by the position before before second target inner space and Pass through in the inner space on the position to form a film before second target positioned at the matrix, by configuring in the matrix The third register of non-film surface side is heat-treated the matrix.

13. a kind of band transparent conductive film substrate, by being separately equipped on the Si film in the front and the back side that are disposed in matrix One transparent conductive film and the second transparent conductive film form, wherein

It will include that hydrogen content in first transparent conductive film is defined as C_H1, second transparent conductive film will be included in In hydrogen content be defined as C_H2In the case where, meet C_H1> C_H2Relational expression, the C_H1And C_H2Unit be atomicity/cm³。

14. band transparent conductive film substrate according to claim 13, wherein

The C_H1It is 10²¹Rank, and the C_H2It is 10²⁰Rank.

15. a kind of solar battery has by being separately equipped with first on the a-Si in the front and the back side that are disposed in matrix thoroughly Band transparent conductive film substrate made of bright conductive film and the second transparent conductive film, wherein

The face side of described matrix is being set as light incident surface, will include the hydrogen content definition in first transparent conductive film For C_H1, will include that hydrogen content in second transparent conductive film is defined as C_H2In the case where, meet C_H1> C_H2Relationship Formula, the C_H1And C_H2Unit be atomicity/cm³。

16. solar battery according to claim 15, wherein

The C_H1It is 10²¹Rank, and the C_H2It is 10²⁰Rank.