JP2704986B2 - Thin film semiconductor device and method of forming the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a photovoltaic element, a photosensitive device for electrophotography, and the like.
Thin-film semiconductor device having a thin-film multilayer structure such as a vice and the like.
A method for forming the same. [Prior art] Conventionally, functional films, especially amorphous to polycrystalline semiconductor films
Are individually adapted from the viewpoint of desired physical properties and applications.
The adopted film forming method is adopted. For example, if necessary, a hydrogen atom (H) or a halogen atom
Amorphous or multi-electrons whose unpaired electrons are compensated by a compensating agent such as
Crystalline non-single-crystal silicon (hereinafter “NON-Si (H, X)”
Abbreviations, especially when showing amorphous lithicon
"A-Si (H, X)", when indicating polycrystalline silicon
Silicon-based deposited films such as “poly-Si (H, X)” films
(Note that microcrystalline silicon is a category of A-Si (H, X)
It goes without saying that you enter
Method, plasma CVD method, thermal CVD method, reactive sputtering method,
Ion plating, photo CVD, etc. have been attempted.
In general, plasma CVD is widely used,
Has been [Problems to be Solved by the Invention] However, the plasma CVD method which has been generally used
The reaction process in forming a silicon-based deposited film by
It is considerably more complicated than the conventional CVD method, and its reactor
There are many unclear points. Also, the parameters for forming the deposited film
Many meters (eg, substrate temperature, flow rate of introduced gas,
Ratio, pressure during formation, high frequency power, electrode structure, reaction vessel
Structure, exhaust speed, plasma generation method, etc.)
Because of the combination of parameters
Becomes unstable and the deposited film formed has a significant adverse effect.
It did not affect the sound. Plus, device specific
Parameters must be selected for each device.
It is difficult to generalize the manufacturing conditions
Was the actual situation. On the other hand, the electrical and optical characteristics of a silicon-based deposited film
To develop something that can be fully satisfied for each application
At present, it is best to form by plasma CVD method.
It is good. However, depending on the application of the silicon-based deposited film, large
Sufficiently satisfy area, film pressure uniformity, and film quality uniformity
Because plasma production must be reproducible, plasma
Mass production of silicon-based deposited films by CVD
A large amount of equipment investment is required for the equipment and for mass production
Management items are complicated, the allowable range of management is narrow, and
Since these adjustments are delicate, these will be improved in the future.
It is pointed out as a problem to be solved. In the case of the plasma CVD method, the arrangement of a substrate on which a film is formed is arranged.
High frequency or microwave in the deposition space
Is generated directly by the
Particles and numerous ionic species can damage the film during the film formation process.
This gives rise to deterioration in film quality and uneven film quality.
You. In particular, in the case of a semiconductor device having a multilayer structure,
It is known that the interface state greatly affects the characteristics of the device.
I have. Therefore, for example, when manufacturing a photoconductor for electrophotography,
In this case, a light reflection preventing layer, a charge injection blocking layer,
When depositing layers, surface protection layers and light absorption enhancement layers,
Gas type, flow rate, plasma discharge intensity, etc. are large for each layer
Due to the difference, the discharge was stopped and a complete gas exchange was performed
And gradually change the gas type, flow rate, and plasma discharge intensity.
To provide a variable layer, or form each deposition layer in a separate deposition chamber.
To improve the state of the interface between each deposition layer.
Thus, the element characteristics are improved. However, this
Satisfactorily changes in device characteristics
No improvement was observed. As mentioned above, in forming a silicon-based deposited film,
There is still a lot to be done and its practical
Energy saving with low cost equipment while maintaining characteristics and uniformity
Development of a forming method that can be mass-produced by measuring energy is awaited
Have been. Especially for thin film transistors, photovoltaic elements, electrophotography
Forming method to improve interface state of thin film multilayer structure such as photoreceptor
The method and interface conditions are good, and thin
There is a strong need for the development of a multilayer film structure. [Means for Solving the Problems] The thin film semiconductor device of the present invention is a semiconductor having a valence electron control.
A thin film semiconductor device having a multilayer structure having a thin film, which contains silicon atoms for forming a deposited film and has a decomposition space (B)
And the chemical interaction with the precursor produced in
Active species generated in the decomposition space (C) to be used;
Are separately introduced into the deposition space (A).
A first semiconductor whose valence electrons are controlled on the formed substrate, and SiH on the first semiconductor. _Four And F _Two And the 1/5 to 50/1 flow
The substrate introduced at a quantitative ratio and kept at room temperature to 700 ° C. is recovered.
Chemical contact in the reaction space of 0.05-10 Torr
A second semiconductor formed on the first semiconductor by
It is characterized by having. The method for forming a thin film semiconductor device according to the present invention is
Multilayer thin film semiconductor with electronically controlled semiconductor thin film
A method of forming a body element, comprising a silicon atom for forming a deposited film and a decomposition space (B)
And the chemical interaction with the precursor produced in
Active species generated in the decomposition space (C) to be used;
By separately introducing them into the deposition space (A).
Forming a valence-controlled first semiconductor on a body
And SiH on the first semiconductor. _Four And F _Two And the 1/5 to 50/1 flow
The substrate introduced at a quantitative ratio and kept at room temperature to 700 ° C. is recovered.
Chemical contact in the reaction space of 0.05-10 Torr
Forming a second semiconductor on the first semiconductor by the
And characterized in that: [Explanation of Functions, etc.] The thin-film semiconductor device according to the present invention and a method of forming the same
According to the results, a multilayer structure with good interface characteristics can be obtained, and
The formation of the laminate is not only energy saving, but also
Satisfies uniformity of film quality and simplifies management and mass production
Without the need for significant capital investment in mass production equipment.
Management items are clarified for mass production, and management tolerance is wide.
In addition, the adjustment of the device is simplified. The gaseous raw material is mixed with a gaseous halogen-based oxidizing agent.
It is oxidized by contact, and
Appropriately selected according to the type, characteristics, application, etc. of the deposited film
Selected. The above gaseous raw materials and gaseous halogen systems
The oxidizer is introduced into the deposition chamber and becomes gaseous when making contact.
It is sufficient that the gas is a liquid or a liquid.
It can be body or solid. The raw material for forming the deposited film or the halogen-based oxidizing agent
Ar, He, N if liquid or solid _Two , H _Two Carry of etc.
Bubble using Argus, adding heat if necessary
A ring is used to form a raw material and
And a halogen-based oxidizing agent as a gas. At this time, the gaseous raw material and the gaseous halogen acid
The partial pressure and mixing ratio of the agent may vary depending on the flow rate of the carrier gas.
Is the raw material and gaseous halogen-based oxidizer for the deposition film formation
It is set by adjusting the vapor pressure of. As a gaseous raw material for forming a deposited film, for example,
Conductive or electrically insulating silicon film or germanium
To obtain a tetrahedral-based deposited film such as an aluminum deposited film.
Straight-chain and branched-chain silane compounds,
Run compounds, chain germanium compounds, etc. are effective.
It can be mentioned. Specifically, as the linear silane compound, Si _n H
_{2n + 2} (N = 1,2,3,4,5,6,7,8), branched chain silane compound
As an object, SiH _Three SiH (SiH _Three ) SiH _Two SiH _Three , Cyclic silanization
Si as compound _n H _2n (N = 3,4,5,6), chain germane
As a compound, Ge _m H _{2m + 2} (M = 1,2,3,4,5) etc.
It is. In addition to this, for example, when creating a deposited film of tin
If SnH _Four Tin hydride as an effective raw material
Can be. Of course, these raw materials are not limited to one kind but may be a mixture of two or more kinds.
Although it can be used in combination, in the present invention, Si
H _Four Is used. Halogen oxidizing agent is introduced into the reaction space.
It is turned into a gaseous state at the same time,
Effective just by contacting gaseous raw material for forming deposited film
It has the property of oxidatively acting, F _Two , Cl _Two , Br _Two , I
_Two Such as halogen gas, fluorine, chlorine, bromine, etc. in the nascent state
Can be mentioned as effective ones, but in the present invention,
And F _Two Is used. These halogen-based oxidizing agents are in gaseous form, and
Apply the desired flow rate and supply pressure together with the raw material gas for forming.
And then introduced into the reaction space and mixed with the raw material.
And make chemical contact to oxidize the raw material.
To efficiently process multiple precursors, including excited state precursors
To be generated. Excited state precursors and other precursors produced
The body is a deposited film on which at least one is formed
Acts as a source of components. The resulting precursor decomposes or reacts to another excited state
A precursor in the excited state or another excited state, or
Or release energy as needed, but leave
Touching the surface of the substrate provided in the deposition space (A)
If the substrate surface temperature is relatively low,
If the deposited film of the workpiece structure has a high substrate surface temperature,
A crystalline deposited film is formed. In the present invention, the deposited film forming process proceeds smoothly.
And a high-quality film having desired physical properties can be formed.
Raw material and halogen-based oxidation which are different as film formation factors
The type and combination of agents, their mixing ratio, the pressure during mixing,
Flow rate, deposition space internal pressure, gas flow type, deposition temperature (substrate temperature
And ambient temperature) are appropriately selected as desired. this
Are organically related and determined independently
Rather, they are determined according to each other based on mutual relations. Departure
In the light, gas for forming a deposited film introduced into the reaction space
The ratio of the amount of the raw material material to the amount of the gaseous halogen-based oxidizing agent is:
In relation to the film formation factors related to the above film formation factors,
It can be determined as desired, but it is preferable
In other words, 1/2 to 100/1 is appropriate, more preferably 1/5 to
Desirably 50/1. The pressure during mixing when introduced into the reaction space is as described above.
Contact between a gaseous raw material and the gaseous halogen-based oxidizing agent
To increase stochastically, higher is better,
It is necessary to determine the optimum value as needed considering the response
good. The pressure at the time of mixing is determined as described above.
However, the pressure at the time of each introduction is preferably 1 ×
Ten ^-7 Atmospheric pressure to 5 atm, more preferably 1 × 10 ^-6 Atmospheric pressure ~ 2
Preferably, the pressure is applied. The pressure in the deposition space (A), that is, a film is formed on the surface
The pressure in the space where the substrate
The excited state precursor (E) and the
Thus, a precursor (D) derived from the precursor (E) is formed.
It is set appropriately as desired so as to effectively contribute to the membrane.
You. The inner pressure of the deposition space (A) is such that the deposition space (A)
If the film is continuous with the gap,
In the reaction space between the raw material substance and the gaseous halogen oxidizer
In relation to the inlet pressure and flow rate of the
Or adjust by adding measures such as using a large exhaust device.
I can do it. Alternatively, a conductor at the connection between the reaction space and the deposition space (A)
When the conductance is small, an appropriate drainage
A vacuum device is provided, and by controlling the displacement of the device,
The pressure in the interval (A) can be adjusted. Also, the reaction space and the deposition space (A) are integrated.
When the reaction position and the deposition position only differ spatially,
Must be pumped differentially as described above, or
What is necessary is just to provide a certain large exhaust device. As described above, the pressure in the deposition space (A) is
Gaseous raw material and gaseous halogen oxidizer introduced between
It is determined in relation to the introduction pressure of
0.001 Torr to 100 Torr, more preferably 0.01 Torr to 30 Torr
r, optimally, it is desirably 0.05 to 10 Torr. For the gas flow type, formation of the deposited film in the reaction space
Such as when introducing raw materials for
Are uniformly and efficiently mixed, and the precursor (E) is efficiently mixed.
To ensure proper film formation
Consider the geometric arrangement of the gas inlet, substrate and gas outlet.
Need to be designed. Suitable for this geometric arrangement
One example is shown in FIG. 1, as described below. The substrate temperature (Ts) during film formation depends on the type of gas used.
And the type of deposited film and the required characteristics
It is set individually as desired, but an amorphous film
When obtaining, preferably from room temperature to 450 ° C, more preferably
Preferably, the temperature is 50 to 400 ° C. Especially semiconductor
Form a silicon deposited film with better properties such as photoconductivity
In this case, the substrate temperature (Ts) should be 70-350 ° C.
desirable. In addition, when a polycrystalline film is obtained,
Should be between 200 and 700 ° C, more preferably between 300 and 600 ° C
desirable. The atmosphere temperature (Tat) of the deposition space (A)
The precursor (E) and the precursor (D) to be
Precursor does not change to unsuitable chemical species and efficiently
As appropriate in relation to the substrate temperature (Ts) so that (E) is produced
Determined as desired. Further, in the present invention, a valence electron-controlled deposited layer is formed.
The method of forming is in a deposition space (A) for forming a deposited film.
Principle for forming deposited film generated in decomposition space (B)
Generated in the decomposition space (C) and the precursor
Introduce the precursor and the interacting active species separately
Forming a deposited film on the substrate.
It is assumed that. Thus, no plasma is used in the deposition space (A)
So the precursors introduced by the deposition parameters of the deposited film and
Introduced amount of active species, temperature in substrate and deposition space, deposition space
Internal pressure and therefore control of deposited film formation
Makes it easy to form a deposited film with reproducibility and mass productivity.
Can be Incidentally, the “precursor” in the present invention refers to a deposited film to be formed.
Deposits can be used as raw materials but remain in the same energy state
A material that cannot or cannot form a film at all
U. An “active species” is one that has a chemical interaction with the precursor.
To give energy to the precursor,
Reacting and forming precursors to form films
The one that plays the role of being able to do things. Therefore,
As the sex species, the constituents of the deposited film to be formed
Or may comprise such components
It does not have to contain an element. In the present invention, the decomposition space introduced into the deposition space (A)
The precursor from (B) has a lifetime preferably of 0.01 seconds or less.
Above, more preferably 0.1 seconds or more, optimally 1 second or more
Are selected and used as desired and the precursor
Components constitute a deposited film used in the deposition space (A)
Constituting the main component. Also, decomposition space (C)
The active species introduced from
Below, more preferably 8 seconds or less, optimally 5 or less
is there. This active species forms a deposited film in the deposition space (A).
At the same time, it is introduced from the decomposition space (B) to the deposition space (A).
Components that are the main components of the deposited film to be formed.
Chemically interacts with the front driver. As a result,
A desired deposited film is easily formed on a desired substrate. According to this method, plasma is generated in the deposition space (A).
The deposited film formed without being raised has an etching action or
Or other adverse effects such as abnormal discharge
There is virtually nothing to do. The atmosphere of the deposition space (A)
By controlling the temperature and substrate temperature as desired
And a more stable CVD method.
One of the differences from the conventional CVD method is that
Use active species that are activated in a space different from (A).
That is. This makes it possible to deposit
The speed can be greatly increased, and in addition,
In this case, it is possible to further lower the substrate temperature,
Industrially large quantities of deposited films with stable film quality and low cost
Can be provided by strike. The active species generated in the decomposition space (C) in the present invention is
By energy such as discharge, light, heat, etc.
Is not only excited, but also contacts with catalyst etc.
Or may be produced by addition. Raw materials introduced into decomposition space (B) in the present invention
As an atom or atom with a high electron-withdrawing property
A group to which a group or a polar group is bonded is used. So
For example, Si _n X _{2n + 2} (N = 1,2,3 ..., X
= F, Cl, Br, I), (SiX _Two ) _n (N ≧ 3, X = F, Cl, Br, I), Si
_n HX _{2n + 1} (N = 1,2,3 ..., X = F, Cl, Br, I), Si _n H _Two X _2n (N =
1,2,3 ..., X = F, Cl, Br, I). Specifically, for example, SiF _Four , (SiF _Two ) _Five , (SiF _Two ) ₆ , (Si
F _Two ) _Four , Si _Two F ₆ , SiHF _Three , SiH _Two F _Two , SiCl _Four (SiCl _Two ) _Five , SiBr _Four , (S
iBr _Two ) ₅ In a gaseous state or easily gasified
Is mentioned. Also, SiH _Two (C ₆ H _Five ) _Two , SiH _Two (CN) ₂ Banks that are also formed
It is used depending on the purpose of use of the film. Heat, light, discharge, etc. in the decomposition space (B)
The precursor is formed by applying the decomposition energy of
It is. This precursor love is introduced into the deposition space (A). this
In this case, the life of the precursor is desirably 0.01 second or more.
In short, it promotes an increase in deposition efficiency and deposition rate,
Active species introduced from the decomposition space (C) in the space (A)
To increase the efficiency of the activation reaction with
Without using discharge energy such as plasma,
(A) Apply energy such as heat or light to the inside or on the substrate
Thus, formation of a desired deposited film is achieved. In the present invention, the active species introduced into the decomposition space (C)
As a raw material for producing _Two , SiH _Four , SiH _Three F, SiH _Three Cl, SiH
_Three Br, SiH _Three In addition to I and the like, rare gases such as He and Ar are exemplified. In the present invention, the decomposition space in the deposition space (A)
From the amount of precursor introduced from (B) and decomposition space (C)
The ratio of the amount of active species introduced depends on the deposition conditions, the species of active species.
It is determined as desired by the type and the like, but preferably 10: 1
~ 1:10 (introduction flow ratio) is appropriate, more preferably 8:
It is desirable to set it as 2: 4: 6. In the present invention, the decomposition space (B) and the decomposition space (C)
The method for producing precursors and active species in
Matter, equipment, discharge energy, heat energy, light
Excitation energy such as energy is used. In addition, a valence electron controlling agent for controlling valence electrons
In order to link, the source material for impurity introduction during layer formation
Introduce into the decomposition space (B) or (C) in gaseous state
Just do it. In that case, not the decomposition space (B),
It is introduced into the decomposition space (C), from which the active species is deposited.
It is preferable to introduce it into the product space (A). The valence electron controlling agent used in the present invention includes
In the case of silicon-based semiconductor film and germanium-based semiconductor film
Is a p-type and a valence electron controlling agent, which acts as a so-called p-type impurity.
Includes elements of Periodic Table Group III A, such as B, Al, Ga, In, Tl
Compounds and n-type valence electron controlling agents, so-called n-type impurities
Elements of Group A of Periodic Table, such as N, P, As, Sb, Bi, etc.
Compounds containing Specifically, NH _Three , HN _Three , N _Two H _Five N _Three , N _Two H _Four , NH _Four N _Three , PH _Three , P _Two H _Four , A
sH _Three , SbH _Three , BiH _Three , B _Two H ₆ , B _Four H _Ten , B _Five H ₉ , B _Five H ₁₁ , B ₆ H _Ten , B ₆ H ₁₂ , Al
(CH _Three ) _Three , Al (C _Two H _Five ) _Three , Ga (CH _Three ) _Three , In (CH _Three ) ₃ Etc.
It can be mentioned as effective. The substrate used in the present invention is formed
What is selected as desired according to the use of the deposited film
If it is, it may be conductive or electrically insulating. Conductivity
As the substrate, for example, NiCr, stainless steel, Al, Cr, Mo, Au,
Metals such as Ir, Nb, Ta, V, Ti, Pt, Pd or alloys thereof
Can be Polyester, polyethylene, etc.
, Polycarbonate, cellulose acetate, polyp
Propylene, polyvinyl chloride, polyvinylidene chloride, poly
Film or sheet of synthetic resin such as styrene or polyamide
Glass, ceramic, and the like are usually used. these
The electrically insulating substrate preferably has at least one surface thereof.
Is conductively treated, and another layer is provided on the conductively treated surface side.
Is desirable. For example, if it is glass, its surface is NiCr, Al, Cr, Mo, A
u, Ir, Nb, Ta, V, Ti, Pt, Pd, In _Two O _Three , SnO _Two , ITO (In _Two O _Three + Sn
O _Two ), Etc. to provide conductive treatment, or
For synthetic resin films such as polyester films, Ni
Gold such as Cr, Al, Ag, Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt
Process by vacuum evaporation, electron beam evaporation, sputtering, etc.
Or laminating with the metal, the surface
Conductive treatment. The shape of the support is cylindrical, bell
Shape, plate shape, etc.
The shape is determined. The base should be considered in consideration of adhesion and reactivity between the base and the film.
It is preferable to select from the following. Furthermore, the difference in thermal expansion between the two
If it is large, a large amount of strain will be generated in the film, and a film in a non-defective room cannot be obtained.
The difference in thermal expansion between the two
It is preferable to use the body selected. The surface condition of the substrate depends on the film structure (orientation) and chain structure.
Is directly related to the occurrence of
It is desirable to treat the surface of the substrate to have a film structure and film structure.
Good. Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
You. First, FIG. 1 shows a method of forming a thin film multilayer structure according to the present invention.
FIG. 1 is a schematic configuration diagram of a deposited film forming apparatus for performing a method.
You. This deposited film forming equipment is composed of the whole equipment, exhaust system and gas supply
It is roughly divided into three types. The device body has a decomposition space (B) and a decomposition space (C).
Is provided. Each of 101 to 108 is filled with gas used for film formation
Cylinders, 101a to 108a are gas supply pipes, respectively.
101b to 108b are respectively used for adjusting the flow rate of gas from each cylinder.
Sflow controller, 101c ~ 108c are each gas pressure
Force meter, 101d to 108d, 101e to 108e and 130 to 133
And 101f to 108f indicate the pressures in the corresponding gas cylinders, respectively.
Pressure gauge. Reference numeral 120 denotes a vacuum chamber, which is provided at the top for introducing gas.
A pipe is provided, and a reaction space is formed downstream of the pipe.
And a base 11 facing the gas outlet of the pipe.
Film formation with substrate holder 112 provided so that 8 is installed
It has a structure in which a space is formed. The piping for gas introduction is
It has a triple concentric arrangement, with a gas cylinder 10
The first gas introduction pipe 109 into which gas from 1,102 is introduced,
A second gas guide into which gas from the cylinders 103 to 105 is introduced.
Gas from the inlet pipe 110 and the gas cylinders 106 to 108 are introduced.
A third gas introduction pipe 111 to be provided. Further, the activation chambers 126 and 12 are provided in the vacuum chamber 120.
7 is connected, a microwave power supply 128 is provided in the activation chamber 126,
A microwave power supply 129 is connected to the activation chamber 127, respectively.
You. And, the microwave supplied from each microwave power supply
By the wave power, the decomposition space (B) in the activation chamber 126 and the
Active species are generated in the decomposition space (C) in the activation chamber 127
Is done. In addition, the active species generating substance is
By 134 and 135, the decomposition space (B) and
(C) is introduced. Each gas introduction pipe, each gas supply pipeline and vacuum chamber
The member 120 is connected to a true vacuum (not shown) through the main vacuum valve 119.
It is evacuated by an empty exhaust device. The base 118 moves the base holder 112 up and down.
Therefore, it should be installed at a desired distance from the position of each gas introduction pipe.
It is. In the case of the present invention, the base and the gas outlet of the gas introduction pipe are connected to each other.
The distance depends on the type of deposited film to be formed and its desired characteristics.
Appropriate in consideration of performance, gas flow rate, internal pressure of vacuum chamber, etc.
It is determined to be in a state like
cm, more preferably, about 5 mm to 15 cm.
New 113 heats the substrate 118 to an appropriate temperature during film formation,
Alternatively, the substrate 118 is pre-heated before film formation, and further,
After film formation, the substrate heating heater is heated to anneal the film.
It is. The substrate heating heater 113 is connected to a power supply 115 by a conducting wire 114.
Power is supplied. For the gas discharge to the reaction space of each gas inlet pipe,
Is positioned farther from the surface of the substrate so that
It is designed to be. In other words, as the outer tube becomes
Each gas inlet pipe is arranged to surround the pipe on the side.
ing. The supply of gas from the pipe cylinder to each inlet pipe
Each is done by a pipeline 123-125. 116 is a thermocouple for measuring the substrate temperature (Ts)
And is electrically connected to the temperature display device 117. A thin film according to the present invention using such a deposited film forming apparatus
For solar cells and electrophotography depending on the method of forming the multilayer structure
A method for manufacturing the image forming member will be specifically described. (Example 1) FIG. 2 shows a solar cell manufactured according to a first example of the present invention.
It is a schematic structure figure of a battery. The solar cell shown in the figure is a glass substrate with a transparent electrode deposited
200, first layer (amorphous silicon doped with boron)
Layer, thickness 500 mm) 201, second layer (non-doped
Amorphous silicon layer, 7000mm thick) 202, 3rd layer (doped phosphorus
Amorphous silicon layer, thickness 500mm) 203, Al electrode
It consists of poles 204. Hereinafter, a method for manufacturing the solar cell will be described in detail. First, the glass substrate 200 on which the transparent electrode was deposited was vacuum-chambered.
Placed on the substrate holder 112 in the chamber 120, evacuated and
Pressure in chamber 120 to 10 ^-6 Torr. And the substrate
Switch on heater 113 for heating, substrate temperature is 280 ℃
It was set to become. Substrate temperature stabilizes at 280 ° C
After the SiF _Four Open gas cylinder 101 and open SiF _Four Gas
20 SCCM was introduced into the activation chamber 126 by a lube operation. Next, hydrogen
Activate hydrogen gas from gas cylinder 106 by operating a specified valve
Introduced 20 SCCM to chemical chamber 127, and _Two H ₆ / H _Two Cylinder (hydrogen
Dilution 1000ppm) 107 to B _Two H ₆ / H _Two Mix gas into activation chamber 127
10SCCM introduced. Internal pressure of vacuum chamber 120 reaches 0.4 Torr
After adjusting the exhaust valve 119 so that
Switch on sources 128 and 129 and place 50 in activation chamber 126
W, supply 50 W of microwave power to the activation chamber 127
Was. Activated species generated in activation chambers 126 and 127 by this
Is introduced into the vacuum chamber 120, and boron is doped.
A first layer 201 of amorphous silicon
Was. After forming the first layer, the microwave radio 128, 129 switch
Off the switch and remove the SiH _Four Gas, H _Two Gas, B _Two H ₆ / H _Two Mixed gas
Are all stopped by a predetermined valve operation, and the vacuum chamber 120 is stopped.
Internal pressure of 10 ^-6 Exhaust until Torr. Next, SiH _Four Open the gas cylinder 102 and operate the specified valve
With SiH _Four The gas is supplied from the 20 SCCM gas introduction pipe 109 to the vacuum chamber 1
20 introduced. Similarly, F _Two / He cylinder (He dilution 10%) 103
To F _Two / He gas from the 200 SCCM gas inlet tube 110 to the vacuum chamber.
Introduced into bar 120. At this time, the internal pressure of the vacuum chamber 120
Is adjusted to 0.8 Torr and the exhaust valve 119 is adjusted and introduced.
SiH _Four And F _Two Non-doped amorphous by oxidation reaction of
A second layer 202 of silicon was formed to a thickness of 7000 mm. After forming the second layer, the SiH _Four Gas and F _Two / He mixed gas
Stop at regular operation, and vacuum chamber 120 ^-6 Exhaust to Torr
I noticed. Third layer 203 of amorphous silicon doped with phosphorus
Is performed by the same operation procedure as that for forming the first layer 201.
Is formed, but B _Two H ₆ / H _Two PH instead of cylinder _Four / H _Two Bonn
Be (H _Two A dilution of 1000 ppm) 107 is used. After forming the first to third layers on the substrate 200 in this manner,
Cool and remove from vacuum chamber 120, on third layer 203
An Al electrode 204 was evaporated. Light (AM-1) is applied to the solar cell thus formed.
When the energy conversion efficiency was measured by irradiation,
Improved by 10%. Table 1 shows the manufacturing conditions and the like described above. (Embodiment 2) FIG. 3 shows an electron manufactured according to a second embodiment of the present invention.
FIG. 2 is a schematic configuration diagram of a photographic image forming member. The image forming member shown in FIG.
Amorphous silicon layer doped with silicon, thickness 3μm) 30
1. Second layer (undoped amorphous silicon layer,
(Thickness: 20 μm) 302, third layer (carbon-containing amorphous silicon)
(Constant layer, thickness 0.5 μm) 303. The first layer 301 and the second layer 302 are operated in the same operation procedure as in the first embodiment.
Formed. The third layer 303 is made of SiF _Four Instead of gas cylinder 101
SiH _Four Gas and CH _Four Gas mixture (SiH _Four / CH _Four = 1/10) Bon
Using a tube, the SiH _Four / CH _Four Mixed gas 110SCCM
Into the vacuum chamber 120 and then F _Two / Ne mixed gas box
Nmbe 103 to F _Two / He mixed gas through 1500 SCCM inlet tube 110
And introduced into the vacuum chamber 120, _Four , CH _Four And F _Two Oxidation of
The third layer 303 was formed by the reaction. About the forming member for electrophotography formed as described above
When the electrophotographic characteristics were measured, the
The charging ability was improved by 10% and the sensitivity was improved by 12% compared with the component. Table 2 shows the manufacturing conditions and the like described above. (Experimental Example 1) The conditions for forming the second layer 202 in Example 1 were changed as shown in Table 3.
A solar cell was manufactured in the same manner as in Example 1 except for the modification.
Was. The second layer 202 was amorphous silicon. Made here
Energy conversion efficiency of the solar cell as in Example 1
And the energy of the same conventional solar cell as in Example 1.
Table 3 shows the measurement results normalized by the conversion efficiency. As a result, when the substrate temperature is 25 ° C, the SiH _Four And F _Two Flow of
When the volume ratio is in the range of 1/5 to 50/1 and the pressure is in the range of 0.05 to 10 Torr.
In the box, the conversion efficiency was 1.04 or more. That is, the substrate
When the temperature is 25 ° C, the conversion efficiency is
The standardized value of the energy conversion efficiency of the solar cell of 1.
Because it is 00, it is improved by 4% or more.
Can be said to be a value with a significant difference in a solar cell. ). However, either the flow ratio or the pressure is in the above range.
Beyond that, the conversion efficiency is less than 1.01, which is
It could not be said that the conversion efficiency was improved. In each table, the dotted line of each condition indicates the value of the present invention.
It is the part that satisfies the numerical range and is within the dotted line in the column of exchange efficiency.
Is when all of the conditions satisfy the numerical range of the present invention
Is the result of (Experimental Example 2) The conditions for forming the second layer 202 in Example 1 were changed as shown in Table 4.
A solar cell was manufactured in the same manner as in Example 1 except for the modification.
Was. The second layer 202 was amorphous silicon. Made here
Energy conversion efficiency of the solar cell as in Example 1
And the energy of the same conventional solar cell as in Example 1.
Table 4 shows the measurement results normalized by the conversion efficiency. As a result, when the substrate temperature is set to 300 ° C, the SiH _Four And F _Two of
The flow rate is in the range of 1/5 to 50/1 and the pressure is in the range of 0.05 to 10 Torr.
In the box, the conversion efficiency was 1.04 or more. That is, the substrate
When the temperature is 300 ° C, the conversion efficiency is 4 in the above range.
% Or more. However, either the flow ratio or the pressure is in the above range.
Beyond the box, the conversion efficiency is less than 1.00,
It could not be said that the conversion efficiency was improved. (Experimental Example 3) The forming conditions of the first embodiment and the second layer 202 were changed as shown in Table 5.
A solar cell was manufactured in the same manner as in Example 1 except for the modification.
Was. Second layer 202 was polycrystalline silicon. Made here
Energy conversion efficiency of the solar cell as in Example 1
And the energy of the same conventional solar cell as in Example 1.
Table 5 shows the measurement results normalized by the conversion efficiency. As a result, when the substrate temperature is set to 700 ° C., the SiH _Four And F _Two of
The flow rate is in the range of 1/5 to 50/1 and the pressure is in the range of 0.05 to 10 Torr.
In the box, the conversion efficiency was 1.04 or more. That is, conversion
Efficiency improved by more than 4%. However, either the flow ratio or the pressure is in the above range.
Beyond the range, the conversion efficiency is 0.96 or less, which is
It could not be said that the conversion efficiency was improved. [Explanation of interface characteristics] In the case of a solar cell, the interfacial characteristics between layers are determined by the open voltage and the filter.
Factor can be measured.
The conversion efficiency reflects these factors, and as a result
The higher the conversion efficiency, the higher the open circuit voltage and fill factor
Is excellent, and the interface characteristics are good.
You. Therefore, the measurement of the conversion efficiency is indirectly the measurement of the interface characteristics.
It will be fixed. The present invention is applied to a solar cell having a thin film multilayer structure.
Indicates that there is no plasma near the substrate when forming each layer,
No damage in the middle, thus improving the interface properties
It is considered that Similarly, in the electrophotographic image forming member,
Improved surface properties, higher charging ability and improved sensitivity
It is thought that it was done. [Effects of the Invention] As described above in detail, the thin film multilayer structure according to the present invention is used.
Since the interface characteristics are improved,
A semiconductor element having excellent characteristics can be obtained. Further, the method of forming a thin film multilayer structure according to the present invention saves energy.
Large area with easy management of film quality while measuring energy
, A deposited film having uniform physical properties can be obtained. Also, production
High quality, electrical, optical, semiconductor
Easy to obtain multilayer structure with excellent physical properties such as
You.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic configuration diagram of a deposited film forming apparatus, FIG. 2 is a schematic configuration diagram of a solar cell manufactured according to a first embodiment of the present invention, FIG. FIG. 4 is a schematic structural view of an electrophotographic image forming member manufactured according to a second embodiment of the present invention. 101 to 108 gas cylinders 101a to 108a gas introduction pipes 101b to 108b mass flow meters 101c to 108c gas pressure gauges 101d to 108d and 101e to 108e, 130, 131, 132, 133 valves 101f to 108f pressure gauges 109, 110, 111 gas introduction tube 112 substrate holder 113 heater for substrate heating 116 thermocouple for substrate temperature monitoring 118 substrate 119 evacuation valves 123 to 125, 134, 135 gas pipes 126, 127 for activation Chambers 128,129 microwave power supply 200 glass substrates with transparent electrodes 201,301 first layer 202,302 second layer 203,303 third layer 204 Al electrode 300 Al substrate

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Isamu Shimizu               2-41-21 Fujigaoka, Midori-ku, Yokohama-shi                (56) References JP-A-59-90923 (JP, A)                 JP-A-60-165728 (JP, A)                 JP-A-60-42766 (JP, A)

Claims (1)

(57) [Claims] What is claimed is: 1. A thin-film semiconductor element having a multilayer structure having a semiconductor thin film of which valence electrons are controlled, wherein said precursor contains silicon atoms for forming a deposited film and is generated in a decomposition space (B); A valence-controlled first semiconductor on a substrate formed by separately introducing the active species generated in the interacting decomposition space (C) into the deposition space (A); SiH ₄ and F ₂ are introduced onto the first semiconductor at a flow rate of 1/5 to 50/1, and the reaction is performed in a reaction space of 0.05 to 10 Torr in which the substrate held at room temperature to 700 ° C. is accommodated. A second semiconductor formed on the first semiconductor by chemical contact. 2. What is claimed is: 1. A method for forming a thin film semiconductor device having a multilayer structure having a semiconductor thin film with valence electron control, comprising a silicon atom for forming a deposited film and generated in a decomposition space (B); And the active species generated in the decomposition space (C) having a chemical interaction with each other are separately introduced into the deposition space (A) to form a valence-controlled first semiconductor on the substrate. And introducing the SiH ₄ and F ₂ onto the first semiconductor at a flow rate ratio of 1/5 to 50/1 to accommodate the substrate maintained at room temperature to 700 ° C. Forming a second semiconductor on the first semiconductor by making chemical contact in a reaction space of 10 Torr.