JPH0480371A - Method and device for formation of deposit film - Google Patents

Abstract

PURPOSE:To stably mass-produce a high-performance photoelectromotive element by use of a tilt-type band profile by allowing the mixed flow of an active seed and a precursor to flow through the space which is surrounded by both a wall provided in the direction along the surface of a base body and this surface of the base body and thereafter exhausting this mixed flow. CONSTITUTION:The N layer of amorphous Si is previously laminated on a base body 101 made of stainless steel. This base body 101 is introduced into an I layer film formation chamber (I). Gas such as H2 and Ar becoming an active seed is introduced from an introduction port 110a. Gas such as SiF4 and GeF4 becoming a precursor is introduced from an introduction port 110b. Prescribed microwave effective power is supplied to the plasma generation chambers 109a, 109b and prescribed trigger is imparted to generate plasma. The active seed and the precursor are introduced into a reaction chamber 113 and a flow 116 is formed. This flow 116 is passed through the space which is surrounded by both a wall 117 provided along the surface of the base body 101 and this surface of the base body 101 and exhausted from an exhaust pipe 114. Thereby an amorphous SiGe film is stably mass-produced by use of a tilt-type band profile wherein Ge concn. in the I layer is made higher as the base body 101 approaches an exhaust port and a band gap is made small according thereto.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field to which the Invention Pertains] The present invention relates to a mass production method and apparatus suitable for forming deposited films containing silicon, particularly photovoltaic elements.

[Description of prior art]

For example, an amorphous silicon film (hereinafter abbreviated as aSi) is used.

) Vacuum evaporation method, plasma CVD method, CVD method, reactive sputtering method, ion blasting method, photo-CVD method, etc. have been tried.
For boat fishing, the plasma CVD method is widely used and commercialized.

However, deposited films formed by these deposited film formation methods generally have poor electrical and optical properties, fatigue properties during repeated use, use environment properties, and productivity including uniformity and reproducibility, and mass production. There is still room for further improvement of the overall characteristics. Among these, in order to develop a deposited film that satisfactorily satisfies each of the electrical, optical, photoconductive, and mechanical properties, it is currently considered best to form it by plasma CVD. Depending on the application of the deposited film, it is necessary to increase the area, make the film thickness uniform, and further improve the uniformity of the film quality, as well as achieve mass production with high reproducibility through high-speed film formation. These problems have also been pointed out as problems that should be improved in the future in the formation of deposited films by this method. Therefore, as a means to solve these problems, a precursor (B), which is a raw material for forming a deposited film produced in an activation space, is placed in a film formation space for forming a deposited film on a substrate. A deposited film forming method has been proposed in which a deposited film is formed on the substrate by introducing an active species (A) that is generated in the chemical space and interacts with the precursor.

Note that "precursor (B)" refers to something that can serve as a raw material for a deposited film to be formed, but is completely or almost incapable of forming a deposited film in its current energy state;
``Activated species (A)'' means a species that causes a chemical interaction with the precursor (B), for example, gives energy to the precursor (B), or chemically reacts with the precursor (B). precursor(
A substance that serves to bring B) into a state in which a deposited film can be formed. Therefore, the active species (A) may contain constituent elements constituting the deposited film to be formed, or may not contain such constituent elements.

This method of forming a deposited film is also suitable for manufacturing photovoltaic devices using high-quality and inexpensive a-3i, and in particular, by assembling a roll-to-roll mass production device using a roll-shaped substrate, Significant improvements in productivity are expected.

On the other hand, among photovoltaic elements, there has been remarkable research and development into improving the performance of solar cells that use amorphous materials containing elements from group II of the periodic table. In order to obtain photoelectric conversion efficiency, materials with high short wavelength sensitivity, such as amorphous silicon carbide (hereinafter abbreviated as aSiC), etc., and materials with high long wavelength sensitivity, such as t4, such as amorphous silicon germanium (hereinafter abbreviated as a-3iGe) are used. ) and other amorphous materials have been developed. Triple-layered solar cells made of these materials are currently showing great results.

In addition, even in a solar cell with a single layer structure, there is a larger band gap (hereinafter abbreviated as Eg) on the light incidence side,
By providing an inclined hand profile that decreases in the film thickness direction, the open circuit voltage ■. , and the conversion efficiency can be improved. This hand profile is shown in FIG. 7(A).

Also, especially intrinsic a-3i, a-5iGe and a-3i
A hand profile has also been devised that promotes the drift of holes with low mobility in one layer in a C film. That is, by creating the hand profile shown in FIG. 7(B), the forward drift of photogenerated holes is promoted and the solar cell OFF is improved. Furthermore, in the hand profile shown in Fig. 7(B), a buffer layer having the same effect as the hunt profile shown in Fig. 7(A) is provided on the light-receiving surface side to create the band profile shown in Fig. 7(C). It becomes possible to obtain a high open circuit voltage and a high FF. In this way, the band profile shown in FIG.
For example, it is possible to create extremely highly efficient photovoltaic elements such as solar cells by making and laminating e and a-5iC films on aSi.

However, in order to mass-produce high-performance photovoltaic devices with such a sloped band profile,
It is necessary to design a mass production method and device with a simple device configuration and a small number of items to be managed.

In order to mass-produce photovoltaic devices with these inclined hand profiles using a roll-to-roll process, it is thought that it would be possible to deal with the problem by installing multiple film-forming chambers in series with stepwise Eg, but the slope Disadvantages include not only not being able to obtain the best graded band profile in the mold, but also increasing the number of film-forming chambers, which increases equipment costs, operating costs, and management items, raising the manufacturing cost of photovoltaic devices. It had

[Purpose of the invention]

An object of the present invention is to provide a deposited film forming method suitable for producing a high-performance photovoltaic device using a tilted band profile in a roll-to-roll mass production device, and an apparatus therefor.

An object of the present invention is to provide a method for forming a deposited film and an apparatus therefor, which can stably mass-produce high-performance photovoltaic elements using a tilted band profile and reduce production costs. It is in.

[Structure of the invention]

The present invention combines active species (A) obtained by activating a gas containing at least hydrogen and at least one or more elements selected from silicon and Group Ⅰ of the periodic table other than silicon (b).
) and a precursor (B) obtained by activating a raw material gas containing a halogen, a flow (AB) obtained by mixing the precursor (B) is guided onto the substrate moving in the direction along the surface of the substrate, and a function is applied onto the substrate. In the method for forming a deposited film, the number of atoms of the element (b) increases with respect to the number of silicon atoms contained in the deposited film obtained on the substrate as it goes downstream with respect to the traveling direction of the flow (AB). This method takes advantage of the feature that the ratio of numbers gradually increases, and this effect will be explained below.

FIG. 8 is a top view of an apparatus for explaining the present invention in detail.

In Figure 8, 1 is an inlet pipe for introducing a gas containing at least hydrogen, which will become the active species (A), and 2 is at least silicon and a gas other than silicon, which will become the precursor (B). This is an introduction pipe through which a raw material gas containing one or more elements (b) selected from the group consisting of halogen and a halogen is passed. 3 is a microwave plasma generating device that activates some or all of these gases to form plasma to generate the active species (A) and the precursor (B). The flow (AB) obtained by mixing these is shown by arrow 5. After the flow (AB) is introduced onto the substrate 6 maintained at a predetermined temperature, it is evacuated from the vacuum chamber 4 to the outside.

Hydrogen and A gas were introduced through the gas introduction tube 1, and 5iFa and GeF4 gas were introduced through the gas introduction tube 2 under the conditions summarized in Table 1, and effective microwave power was applied to the microwave plasma generator 3. When a predetermined amount is applied, the active species (A
) and activated S i Fa and G
Precursors corresponding to the precursor (B) produced from eF4 are respectively generated and meet at the outlet of the introduction tube 2 to deposit an a-3iGe film on the substrate 6. #7059 glass substrate made by Corning was installed on the base of No. 6, and the flow (AB
) The bandgap distribution was determined by T auc plot in the direction of flow. Furthermore, an aluminum substrate was placed on the 60 substrate, and the Ge5 degree distribution in the film was similarly determined by XMA in the direction of the flow (AB). These are summarized in the graph of Figure 9.

In FIG. 9, the horizontal axis X is scaled in the direction of the flow (AB), and the vertical axis is Eg and aetyB in the film, respectively.
degree. From FIG. 9, as the flow progresses downstream in the direction of the flow (AB), the Ge concentration in the deposited film obtained on the substrate changes from about 2 (atomic%) to about 40 (atomic%).
ic%), and along with this, E
It can be seen that g also decreases linearly from 1.7 (eV) to 1.4 (eV).

Similarly, an example of a-3iC film formation will be given. Gas introduction pipe 1
From No. 02, CF a was introduced in place of GeFa, and an a-3iC film was formed on the substrate according to the predetermined forming conditions summarized in Table 1. Similar to the case of the a-3i'Ge film, the distribution on the substrate of 6 was investigated in terms of Eg and C concentration in the film, and as in the case of the a-5iQe film, the band gap is 1.7 (eV) to 2.1
(eV), and the C concentration in the film also increases from about 3 (atomic%) to 20 (atomic%).
mic%).

The present inventors thus discovered that the ratio of the number of atoms of the element (b) to the number of silicon atoms in the deposited film deposited on the substrate gradually increases as it goes downstream in the traveling direction of the flow (AB). By applying this knowledge to a roll-to-roll mass production device, it was possible to mass-produce solar cells with a sloped band profile.

That is, according to the present invention, first, a wall is provided along the base body, and one end of the wall is provided with an exhaust pipe directly connected to an exhaust device,
Further, by providing an inlet at the other end through which the active species (A) and the precursor (B) can be mixed and introduced, the flow (AB) can be directed in the direction along the surface of the substrate. It becomes possible to make.

Further, the flow (AB) is introduced perpendicularly to the surface of the base, and a gas (C) whose flow direction is at an angle of 10° or more and 90° or less with respect to the flow direction of the flow (AB) is introduced. Accordingly, the direction of the flow (AB) can be changed from a direction perpendicular to the surface of the substrate to a direction along the surface of the substrate. At this time, it is also possible to activate the gas (C) in advance and introduce it, thereby achieving a cleaning effect by pre-sputtering the substrate surface and a reaction between the active species (A) and the precursor (B) on the substrate surface. It can be expected to have the effect of assisting.

Furthermore, the direction of the flow (AB) is introduced to the surface of the substrate at an angle between 30° and 90°, so that the angle between the direction and the normal to the surface of the substrate is such that the flow (AB) is directed along the surface of the substrate. It is also possible to flow in the opposite direction.

Hereinafter, the present invention will be explained in detail based on specific examples.

Figures 1 (A), 1 (B), and 1 (C) show schematic diagrams of the mass production apparatus for photovoltaic devices of the present invention, and especially Figure 1 (C) is a It is a drawing that best represents the features of the invention. In Figure 1 (A), 1
01 is a stainless steel substrate, and 102 and 103 are rolls for sending out and winding up 101, respectively. 102 and 103 are in the atmosphere. The series number 104 is a vacuum chamber for mass production of solar cells,
104 is a load chamber that serves both preliminary exhaust and preliminary heating.

104 (N).

104 (1) and 104 (P) are film forming chambers for N layer, 1 layer, and P layer, respectively. 104(0) is a vapor deposition chamber for a transparent conductive film, and each chamber is equipped with an independent exhaust unit.

Subsequently, FIG. 1 (B) shows 104 (N) and 104
It is a drawing for explaining the film-forming chamber used for (P). In the figure, 105 is a glass tube made of quartz, into which hydrogen or a gas containing hydrogen can be introduced. On the other hand, 106 is a glass tube made of quartz, which has a coaxial double tube structure with 105, into which silicon or a gas containing elements of Groups Ⅰ, Ⅲ, and V of the periodic table other than silicon and halogen is introduced. Is possible. 107 is a plasma generator equipped with a microwave power supply unit (not shown);
This is a device for converting part or all of the gas introduced from 05 and 106 into plasma. Further, instead of the microwave plasma generator 107, an RF plasma generator can be used. 108 is an infrared lamp for heating the stainless steel roll substrate 101;
1 to a predetermined temperature and maintain it.

In the chamber 104(N), the N layer is transferred to the chamber 104(N).
In P), a P layer is created, but to explain the N layer as an example, 101 is heated to a predetermined temperature in advance, hydrogen and Ar are added to the quartz glass tube 105, and 5iFn is added to the quartz glass tube 106. Flowing a predetermined amount of pH 3 As described in detail of the present invention, when a predetermined effective microwave power is supplied from a microwave power source to generate plasma, Hz+A r,
A part or all of S + F4 and PHff are activated, combine at the outlet of the quartz glass tube 106 and are transported onto the quartz glass tube 101 to form an N-type a-3i film on the quartz glass tube 101 .

Next, the preparation of PL of microcrystal silicon (hereinafter abbreviated as μC3i) will be explained. P-layer production differs from N-layer production in that B F s is introduced from 106 instead of PH, and the H2 flow rate is increased by about 50% as a condition for producing μC-3i. In this way, μC
Although it is possible to deposit a -3i P layer on 101, the conditions for forming the N layer and the P layer are summarized in Table 2.

Next, a method for forming one layer, which is a feature of the present invention, will be explained by taking a graded a-3iGe layer as an example.

Figure 1 (C) is 1 for detailed explanation of the present invention.
FIG. 2 is a schematic diagram of a layer deposition chamber 104(+). In the same figure, the stainless steel substrate 101 is in the N layer deposition chamber with a-3i N
The stacked layers are sent to 104(1). 10
9a, b are microwave cavity type cavity resonators, 11
1 a, b are Me-7 windows, 112 a, b are alumina windows,
110a and 110b are gas introduction ports. A predetermined gas is supplied from 110a and 110b, and a predetermined effective microwave power is supplied to 109a and 109b, as shown in Table 3. ), by applying a predetermined trigger, plasma is generated in both cavities 109a and 109b, and active species and precursors are introduced into the film forming chamber 113 through the meshes 11a and 109b, respectively, creating a flow 116. This flow 116 passes through a space surrounded by a wall 117 along the surface of the base 101 and the surface of the base 101, and is further exhausted to an exhaust system through an exhaust pipe 114.

The one-layer A-3 ice film created in this way has a distribution in which the degree of c e tH contained in the one layer gradually increases as it approaches the exhaust port, and along with this, the Eg
tends to become smaller.

Therefore, one layer of solar cells as shown in FIG. 2 is laminated on a rolled stainless steel substrate on which N layers have been laminated in advance. Next, 104(1) is 101 which is 10.
After predetermined P layers are laminated in 4(P), 104(0
), transparent conductive films are laminated under predetermined conditions and wound around 103.

FIG. 2(A) is a schematic diagram of the mass-produced solar cell of this example, and FIG. 2(B) shows the profile of one layer of Eg according to this example. 201 is stainless steel base incense cloth, 202
N, 2021.202P are respectively aSi N layer and a-3i
They are a Gell oblique I layer and a μcSi P layer. In this way, after the precursor and the active species associate, the resulting flow is guided in the direction along the surface of the substrate, thereby facilitating the a
It is possible to create a diagonal layer of 3iGe.

As shown in Table 5, the a-8iGe solar cell produced in this way has an Eg of 1.4 (eV
) photoelectric conversion efficiency η is 8 compared to the a-3iGe solar cell.
．． It was possible to improve it from 0 (%) to 9.2 (%).

Next, in Example 2, an a-5rGe solar cell with a buffer layer and a reverse slope band profile will be described. First, in the same way as in Example 1, this example was carried out using the mass production apparatus shown in FIG. Explain.

In the figure, 301 (F) and (R) are gas introduction pipes, 302 (F) and (R) are hydrogen or hydrogen-containing gas introduction pipes, and 303 (F) and (R) are Si and the periodic table. This is an introduction pipe for a gas containing Group Ⅰ elements and halogen. (F) and (R) in each drawing mean a Front part and a Rear part, respectively, when viewed from the introduction direction of the base body 101.

304 is a microwave plasma generator (incidental equipment such as power supply not shown). 305 is pyrolysis heater 3.07
(F), (R), 30B (F) and (R) are arrows indicating the main flow direction of gas, respectively.

A tungsten lamp 309 maintains the substrate 101 at a predetermined temperature. The predetermined gas flow rate, microwave effective power, and heater temperature are summarized in Table 4.

The mixed gas of H2 and Ar introduced from 302 (F) becomes a plasma state at 304 and generates many active hydrogen atoms, and at 306 (F), it is introduced from 303 (F) and is thermally decomposed by 305. The precursors generated from the mixed gas of 5itFb and G e Fa combine, undergo a chemical reaction, and are transported in the flow direction shown in 308 (F), forming a substrate 101 (on which an N-type a-Si layer has already been laminated). ) is first introduced vertically. Furthermore, 301
From (F), when a predetermined Ar is introduced at a predetermined angle θ,
It is possible to change the flow introduced perpendicularly to the substrate 101 in the direction shown by the arrow 307(F). In FIG. 3, the gas flow shown at 308(R) can be similarly generated by each gas introduction pipe installed substantially symmetrically. The flow rate of the gas introduced from 301 (F) and 301 (R), θ, and θ can be adjusted appropriately to optimize the buffer layer and the reverse gradient layer, and θ and θ8 can be adjusted as appropriate. It is possible to adjust within the range of 10° or more and 90° or less.

As a result of this optimization, the production conditions were as summarized in Table 4. FIG. 4 shows the Eg profile in the film thickness direction of a reverse slope type a 5iGe solar cell having a buffer layer produced under these production conditions.

In addition, as summarized in Table 5, Eg-1 (conventional example),
At 4 (eV), a large effect in conversion efficiency of 8.0 (%) to 10.0 (%) is recognized compared to an a-5iGe solar cell without tilting.

Next, we will show that the present invention is effective in a roll-to-roll mass production device for triple solar cells having the configuration shown in FIG. 5A and 5E are schematic diagrams of this embodiment. In the figure, 504 is a preheating chamber, 505 (N
), (IL (P), 506 (N), (1), (P
), 507 (N), (1), and (P), the subscript (N) indicates the N layer, the subscript (1) indicates the single layer, and the subscript (P) indicates the P layer. shows.

A schematic diagram of 505(1) and 506(1) is shown in FIG. 5(B), in which a buffer layer and a bottom layer and a middle layer of reversely graded a-3iGe are created, respectively. The schematic diagram of 507(+) is the fifth
In the figure (C), a buffer layer and a top layer of reverse slope type a-3iC are respectively created. 508 is a vapor deposition chamber for a transparent conductive film. 5 (B) and 5 (C), the subscripts (F) and (R) of each figure number are the Front side and the Rear side with respect to the introduction direction of the substrate 501, as in Example 2. It is. 509 (F), (R), 5 in Figure 5 (B)
10 (F).

(R) is each gas introduction tube, 511 (Fn), (R) is a microwave plasma generator, and 513 is a tungsten lamp for heating the substrate. It is a corner.

Further, in FIG. 5(C), 513 and 514 are gas introduction pipes, and 515 is a plasma generator.

θ is the angle between the gas introduction pipe and the substrate 501.

Table 6 summarizes the film forming conditions in each I layer film forming chamber.

First, the bottom layer buffer layer and the reversely graded a-3iGe
The first layer of will be explained. In FIG. 5(B), 50
Gases containing hydrogen are introduced from 9 (F) and (R), respectively, and are activated by the microwave plasma generators of 511 (F) and (R) to form a plasma state, respectively.
510 (F), (R
) respectively associate with SiFa and GeF introduced from 512 (F
) and (R) to form a deposited film of a-3iGe on the substrate 501, the band gap of which tends to become smaller as it moves farther from the gas introduction tube. As in the previous embodiment, the base body 501 has N layers laminated in advance. θ and θ are the gas introduction pipe and the base 50
1, but a reverse slope type a- with a buffer layer.
The angle can be adjusted appropriately from a minimum of 10° to a maximum of 90° in accordance with the optimization of the 3iGe solar cell. In a triple cell, it is currently considered optimal for the bottom layer to have a high infrared sensitivity and a small bandgap, for example, about 1.40 (eV). Optimization can be achieved by setting the gap to 1.40 (eV) and that of the middle layer to 1.65 (eV).

In this embodiment, the balance of the flow rates of each gas, the effective microwave power, and θ1. Optimization was attempted by setting the conditions for θ.

In Table 3, for convenience, since the device configurations of the bottom layer and the middle layer are almost the same, a dash is added after the figure number as the figure number of the middle layer. The reversely sloped band profiles of the bottom and middle buffer layers are basically the same, but the particular difference is that the bottom layer is designed to have a smaller Eg in order to make the long wavelength sensitivity stronger. For this reason, the flow rate of GeF is 6 times that of the middle layer, and the thickness of the bottom layer is approximately twice that of the middle layer, so the effective power of the microwave is 5 times that of the middle layer. It is somewhat larger.

Next, creation of the top layer will be explained. What is characteristic here is that with only one gas inlet pipe, it is possible to create a single layer of an inverted slope type having an a-5iC layer and seven fur layers as shown in FIG.

In FIG. 5(C), hydrogen and A are introduced from the gas introduction pipe 513.
r is introduced through 514, converted into plasma by a microwave plasma generator 515, and introduced into the film forming chamber. 5iFn and CF are introduced from the gas introduction pipe 514 and are caused to associate with each other through a chemical reaction to form flows 516 and 517. make. The flow 516 flows in the opposite direction to the direction of movement of the base body 501,
517 flows in the forward direction. In the region sandwiched between 516 and 517, aS with less C (carbon) component on 501
An iC film is deposited, and as it advances in the flow direction of 516, an a-3 iC film with a large C component is deposited on 501. Similarly, in the flow direction of 517, a-3iCIIg with a larger C component is deposited on 501 as it advances in the flow direction.

In this way, it is possible to create a reversely graded a-3iC top layer with a buffer layer as shown in FIG.

Also, the positioning in the film thickness direction where Eg is minimum is as follows:
This is possible by appropriately selecting the angle θ formed by the angle θ.

A transparent conductive film is deposited at 508 on the base 501 on which the bottom, middle, and top layers are laminated in this order in this manner, and the film is wound up with a roll 503 . The conversion efficiency of the solar cell produced as described above, that is, a triple-structured solar cell in which each layer had a buffer layer and a reversely inclined band profile, was 13.5 (%).

On the other hand, a -S i G e (Eg-1, 40 (eV
)).

a-5i (Eg=1.70 (eV)), and a-5iC
Compared to the conversion efficiency of the triple solar cell obtained using (Eg = 2.2 (eV)), which was 12.1 (%), the conversion efficiency was improved by 1.4 (%). I understand.

Table 4 a-3i of graded band profile with buffer layer
Conditions for creating a single layer of Ge 6 Conditions for creating an inverted triple structure solar cell with a front buffer layer [Effects of the invention] 7 As explained above, especially for a-3iGe and a-3iC
According to the present invention, when producing a high-performance photovoltaic device using a graded band profile using roll-to-roll mass production equipment, the graded bandgap is of good quality and slopes smoothly. Not only does it eliminate the need to increase the number of film-forming chambers, it also reduces equipment investment, reduces equipment operation management items, provides stable product production, and reduces production costs. This has the effect of supplying high-performance photovoltaic elements to the market at low cost.

[Brief explanation of drawings]

FIG. 1 (A) is a schematic diagram of a basic solar cell mass production apparatus necessary for carrying out the present invention. 1st (B) IIJ
is a cross-sectional view of a basic film forming chamber for creating the N layer and P layer of a solar cell. FIG. 1 (C) is a sectional view of a film forming chamber for forming a layer (1) explained in Example 1 of the present invention. The second M is the structure of the solar cell explained in Example 1 and lJi
A diagram showing a band profile of. FIG. 3 is a schematic diagram of a film forming chamber for forming one layer of a solar cell explained in Example 2. FIG. 4 is a diagram of the configuration and band profile of the solar cell of the same example. Figure 5 (A) is a schematic diagram of the mass production equipment for creating a triple solar cell in Example 3, and Figure 5 (B) is a diagram for creating the a-3iGe bottom layer and middle layer in the same Example. Figure 5 (C) is a schematic diagram of a film forming chamber for forming the top layer. FIG. 6 is a diagram showing the configuration of the triple solar cell of the same example and the reverse slope type band profile having one buffer layer each. 7(A), 7(B), and 7(C) are diagrams showing band profiles of conventional photovoltaic elements, respectively. Each is a PIN type with a light-receiving surface on the P-type side, and the band profile of one layer is shown. Figure 7 (A) shows an inclined type in which Eg is large on the light-receiving surface side and decreases smoothly in the film thickness direction. Figure 7 (B) shows a reverse tilt type designed to encourage the drift of holes in the valence band. Figure 7(C) is the 7th
(B) shows a reverse slope band profile with a buffer layer further provided on the light-receiving surface side in the figure. FIG. 8 is a schematic diagram of a deposited film forming apparatus for explaining the present invention in detail, and FIG. 9 shows a-5iGe formed using this apparatus.
2 is a graph showing the distribution of Eg on the substrate 6 of the film and the degree of Ge presence in the film. In FIG. 1 (A), 101...Stainless steel substrate base, 102...Substrate feeding roll, 103...Substrate winding roll, 104...Preheating chamber, l04(N)...N Layer deposition chamber, 104(1)...Layer deposition chamber, 104(P)...P layer deposition chamber, 104(0)...Transparent conductive film deposition chamber. In Fig. 1 (B), 105, 106... gas introduction pipe, 107... plasma generator, 108... infrared lamp. In FIG. 1 (C), 09a, 109b... cavity type plasma generation chamber,
10a, I10b--Gas inlet, 11a,
11 l b-... Mesosh, 12a, 112b.
... Alumina ceramics, 13... Reaction chamber for precursor and active species, 14... Exhaust pipe, 115... Tungsten lamp,
16...Arrows indicating the flow of active species and precursors, 17...
- A wall provided in a direction along the surface of the base 101. In FIG. 2 (A), 01...Stainless steel substrate base, 02(N)-a-5i N layer, 02(+)...a- with a sloped band profile.
One layer of 5iGe, 02(P)... PM of μC-3iC. In Fig. 3, 01 (F), (R)...gas introduction pipe, 02 (F)
, (R)...Introducing pipe for hydrogen or a gas containing hydrogen, 303 (F), (R)...Introducing pipe for a gas containing halogen and an element of group II of the periodic table, 304...Microwave Plasma generator, 305...
- Heater for pyrolysis 306 (F), (R)... Meeting space of precursor and active species, 307 (F), (R)... Arrow indicating gas flow, 30 s (F), ( R)...Arrow indicating the flow of precursor and active species, 309...Tungsten heater θ2. θ5...Angle between the base and the gas introduction pipe. In FIG. 4, 401... Base of stainless steel substrate, 402 (N) = -a-5i N layer, 402(1).
・・・a of reverse slope band profile with buffer layer
-S i G e layer, 402(P)...μC-3i
P layer of C, 403...transparent conductive film. In FIG. 5(A), 501...base body of stainless steel roll substrate, 502...
・Substrate feeding roll, 503...Substrate winding roll, 504...Preheating chamber, 505(N), 506(N), 507(N)-a-3i
N-layer film formation chamber, 505(1), 506(1)... a-S r G e + with a reverse sloped band profile with a buffer layer
507(1)... Single layer deposition chamber for a-5iC with a reverse sloped band profile having a buffer layer,
505(P), 506(P), 507(P)...μC
-5iC P layer deposition chamber, 508...Transparent conductive film deposition chamber. In Figures 5(B) and 5(C), 509(F),
(R), 513... Introducing pipe for hydrogen or a gas containing hydrogen, 510 (F), (R), 514... Introducing pipe for a gas containing halogen and an element of group Ⅰ of the periodic table, 511 ( F), (R), 515... Microwave plasma generator, 512 (F), (R), 516.517... Arrow indicating the flow of precursor and active species, 513... Infrared lamp, θ4. θ5. θ...Angle between the gas introduction pipe and the board, X
f+X! ... Distance from the chamber wall indicating the position of the gas introduction pipe in the 507(1) film forming chamber. In Fig. 6, 601...Stainless steel roll substrate, 602(N), 603(N), 604(N)-a-3i
N layer, 602(I), 603(1)...a-5iGe with reverse sloped band profile with buffer layer
604(+)...1 layer of a-5iC with a reverse sloped band profile with a buffer layer, 602(P), 603(P), 604(P)...μC
-5iC P layer, 605...transparent conductive film. In Fig. 8, l... gas introduction pipe, 2... gas introduction pipe, 3... microwave plasma generator, 4... vacuum chamber 5... mixed flow of active species and precursors. An arrow indicating the direction of 6...Base. Patent applicant Canon Co., Ltd. No. 1 (A) Zuka 2 (A) Fig. 2 (B) Fig. Fig. Fig.

Claims (8)

[Claims] (1) Activate the activated species (A) obtained by activating a gas containing at least hydrogen and a source gas containing at least silicon, one or more elements selected from Group IV of the periodic table other than silicon, and halogen. Deposited film formation in which a flow (AB) obtained by mixing the precursor (B) obtained by oxidation is guided onto a substrate moving in a direction along the surface of the substrate, and a functional deposited film is formed on the substrate. In the method, the flow (AB
) flows through a space surrounded by a wall provided in a direction along the surface of the substrate and the surface of the substrate and then is exhausted. (2) Activate the activated species (A) obtained by activating a gas containing at least hydrogen and a source gas containing at least silicon, one or more elements selected from Group IV of the periodic table other than silicon, and halogen. Deposited film formation in which a flow (AB) obtained by mixing the precursor (B) obtained by oxidation is guided onto a substrate moving in a direction along the surface of the substrate, and a functional deposited film is formed on the substrate. In the method, the gas (C) does not contain at least an element of Group IV of the periodic table, and the angle between the direction of flow of the gas (C) and the direction of the flow (AB) is 10° or more and 90° or less. A method for forming a deposited film characterized by introducing the method as follows. (3) The deposited film forming method according to claim (2), characterized in that the gas (C) is activated in advance. (4) Activate the activated species (A) obtained by activating a gas containing at least hydrogen and a source gas containing at least silicon, one or more elements selected from Group IV of the periodic table other than silicon, and halogen. Deposited film formation in which a flow (AB) obtained by mixing the precursor (B) obtained by oxidation is guided onto a substrate moving in a direction along the surface of the substrate, and a functional deposited film is formed on the substrate. In the method, the flow (AB
) and the normal to the surface of the substrate, the angle between the direction and the normal to the surface of the substrate is 30° or more and 90° or less. (5) Activate the activated species (A) obtained by activating a gas containing at least hydrogen and a source gas containing at least silicon, one or more elements selected from Group IV of the periodic table other than silicon, and halogen. Deposited film formation in which a flow (AB) obtained by mixing the precursor (B) obtained by oxidation is guided onto a substrate moving in a direction along the surface of the substrate, and a functional deposited film is formed on the substrate. In the device, the flow (AB
) flows through a space surrounded by a wall provided in a direction along the surface of the substrate and the surface of the substrate and then is exhausted. (6) Activate the activated species (A) obtained by activating a gas containing at least hydrogen and a source gas containing at least silicon, one or more elements selected from Group IV of the periodic table other than silicon, and halogen. Deposited film formation in which a flow (AB) obtained by mixing the precursor (B) obtained by oxidation is guided onto a substrate moving in a direction along the surface of the substrate, and a functional deposited film is formed on the substrate. In the apparatus, the gas (C) that does not contain at least an element of Group IV of the periodic table is further prepared such that the angle between the flow direction of the gas (C) and the flow direction (AB) is 10° or more and 90° or less. A deposited film forming apparatus characterized by having means for introducing a deposited film into a deposited film. (7) The deposited film forming apparatus according to claim (6), wherein the gas (C) is activated in advance. (8) Activate the activated species (A) obtained by activating a gas containing at least hydrogen and a source gas containing at least silicon, one or more elements selected from Group IV of the periodic table other than silicon, and halogen. Deposited film formation in which a flow (AB) obtained by mixing the precursor (B) obtained by oxidation is guided onto a substrate moving in a direction along the surface of the substrate, and a functional deposited film is formed on the substrate. In the device, the flow (AB
) is introduced so that the angle between the direction of the flow (AB) and the normal to the surface of the substrate is 30° or more and 90° or less.