JP2855300B2 - Non-single-crystal germanium semiconductor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an amorphous germanium semiconductor (including a microcrystalline germanium semiconductor), a polycrystalline germanium semiconductor, an amorphous silicon germanium semiconductor (including a microcrystalline silicon germanium semiconductor), and a polycrystalline silicon germanium. The present invention relates to a non-single-crystal germanium semiconductor such as a semiconductor.

[0002]

2. Description of the Related Art Silicon semiconductor films, such as amorphous silicon semiconductors and polycrystalline silicon semiconductors, have been applied to photoreceptive members for electrophotography, solar cells, thin film transistors, photoelectric conversion elements such as photosensors, and semiconductor elements. I have. In particular, in solar cells, further improvement in film quality is desired for problems such as light degradation and improvement in conversion efficiency.

Recently, in an amorphous silicon semiconductor used for a normal solar cell, a thin film transistor, or the like, the average radius of microvoids present in the semiconductor film is 4 to 4.
It has been reported that the density is 2 × 10 ¹⁹ (cm ⁻³ ) or more at 5 ° (“Characterizat”).
ion of microvoids in devi
ce-quality hydrogenated a
morphous silicon by small
-Angle X-ray scattering a
nd infrared measurement
s', A. H. Mahan, D .; L. Williams
on, B. P. Nelson and R.S. S. Cra
ndall, Physical Review BV
ol. 40, no. 17, 15 Dec. 1989-
I, 12012; 'Small-angle X-ra
y scattering from microvi
ds in the a-SiC: Halloy ',
A. H. Mahan, B .; P. Nelson and
D. L. Williamson, IEEE. TRANS
ACTIONS ON ELECTRON DEVIC
ES VOL. 36, no. 12, DEC. 1989,
2859). The paper also suggests that these microvoids are related to the band edge state and the recombination center. Furthermore, in these microvoids,
A hydrogen atom is attached and this hydrogen atom can move in the void. It is suggested that this is related to light degradation.

[0004] However, there has been no report on a non-single-crystal germanium semiconductor as described above.

According to the research conducted by the present inventors, it has been found that a conventional non-single-crystal germanium semiconductor has a micro void.
(void) shape to STM (scanning tun)
observing with the "nelling microscope"
Circular and elliptical shapes with a depth of 1 to 4 atoms were observed.
In addition, it was estimated from the arrangement of the atoms around the microvoids that there was a stress around the microvoids.

Further, similarly to the above-mentioned paper, SAXS (sma
ll angle X-ray scatterin
When measured by the g) method, in the conventional non-single-crystal germanium semiconductor, the average radius of microvoids was 4 to 7 ° and the density was 2 × 10 ¹⁹ (cm ⁻³ ) or more. As described above, in the conventional non-single-crystal germanium semiconductor, it is considered that the bond of a considerable number of germanium atoms has a strain considerably deviated from the bond of the crystal.

[0007] Such a distortion of the germanium atom prevents the activation of the impurity when the impurity is doped, and lowers the doping efficiency. In some cases, impurities are trapped in the microvoids and the impurities are bonded in an inactive state. Furthermore, the mobility of the electric charge is also reduced due to such microvoids and the strains associated with the microvoids.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide an amorphous germanium semiconductor, a polycrystalline germanium semiconductor, an amorphous silicon germanium semiconductor, a polycrystalline silicon germanium semiconductor, etc., in which the average radius of microvoids is small and the density is low. A non-single-crystal germanium semiconductor.

Another object of the present invention is to provide a non-single-crystal germanium semiconductor in which impurities hardly diffuse.

Another object of the present invention is to provide a non-single-crystal germanium semiconductor with high impurity doping efficiency.

Another object of the present invention is to provide a non-single-crystal germanium semiconductor having good adhesion when a plurality of non-single-crystal germanium semiconductor layers are stacked.

Another object of the present invention is to provide a non-single-crystal germanium semiconductor capable of forming a junction exhibiting good characteristics.

Another object of the present invention is to provide a non-single-crystal germanium semiconductor which can be sufficiently used even in a thin film.

Another object of the present invention is to provide a non-single-crystal germanium semiconductor film in which electric charges are easily transferred.

[0015]

DISCLOSURE OF THE INVENTION The present invention has been completed as a result of intensive studies by the present inventors to solve the problems in the prior art and to achieve the above object.

In the non-single-crystal germanium semiconductor film of the present invention, in a non-single-crystal germanium semiconductor film containing at least germanium atoms and hydrogen atoms and / or halogen atoms, the average radius of microvoids present in the semiconductor film is reduced. 3.5 × or less and density 1 × 10 ¹⁹ (cm ^-3 )
It is characterized as follows.

The non-single-crystal germanium semiconductor of the present invention having the above-described structural characteristics has an effect that impurities added to the semiconductor are difficult to diffuse.

Further, the non-single-crystal germanium semiconductor of the present invention has the effect that the impurity doping efficiency is high.

Still further, the non-single-crystal germanium semiconductor of the present invention has an effect that good adhesion is obtained when a plurality of non-single-crystal germanium semiconductor layers are stacked.

In addition, the non-single-crystal germanium semiconductor of the present invention has an effect that a junction exhibiting good quality can be formed.

Still further, the non-single-crystal germanium semiconductor of the present invention has an effect that dielectric breakdown is difficult even in a thin film.

In addition, the non-single-crystal germanium semiconductor of the present invention has an effect that charges can easily move.

[0023] In addition, the non-single-crystal germanium semiconductor of the present invention has an effect that the interface level is small when a junction is formed with a non-single-crystal silicon semiconductor.

Further, the forbidden band width can be controlled by adding silicon atoms to the non-single-crystal germanium semiconductor of the present invention.

The structure of the non-single-crystal germanium semiconductor of the present invention will be described in more detail.

In the non-single-crystal germanium semiconductor of the present invention, when the non-single-crystal germanium semiconductor is an amorphous germanium semiconductor, the content of hydrogen atoms contained in the semiconductor is preferably 1 to 30 at%, Optimally 5
２５25 at%. The hydrogen bonding state is Ge
-H bond (1880 cm ^-1 peak in IR spectrum) and GeH ₂ bond (1980 cm ^-1 peak in IR spectrum) (assuming Gaussian distribution at each peak) [G
[eH ₂ ] / [GeH] is preferably 1/20 or less.

Further, the halogen atom (fluorine atom is particularly preferable) contained in the amorphous germanium semiconductor of the present invention is preferably 0.1 to 10 at%, and most preferably 0.1 to 10 at%.
1 to 5 at%.

Furthermore, it is preferable that the average radius of the microvoids contained in the semiconductor of the present invention is 3.5 ° or less and the density of the microvoids is 1 × 10 ¹⁹ (cm ⁻³ ) or less.

On the other hand, when the non-single-crystal germanium semiconductor of the present invention is a polycrystalline germanium semiconductor, the content of hydrogen atoms contained in the semiconductor is preferably 0.1 to 10 a.
t%, optimally 0.1 to 5 at%. The hydrogen bonding state is GeH bonding (188 in the IR spectrum).
0 cm ^-1 peak) and SiH ₂ bond (1 in the IR spectrum).
(GeH ₂ ) / [GeH] is preferably 1/10 or less (assuming a Gaussian distribution at each peak).

Further, the halogen atom (fluorine atom is particularly preferable) contained in the polycrystalline germanium semiconductor of the present invention is preferably 0.1 to 5 at%, and most preferably 0.1 to 5 at%.
Ａｔ3 at%.

Further, the average radius of the microvoids contained in the semiconductor of the present invention is preferably 3.5 ° or less, and the density of the microvoids is preferably 1 × 10 ¹⁹ (cm ⁻³ ) or less. .

In the present invention, by setting the average radius of the microvoids to 3.5 ° or less, the possibility of the formation of a Ge—H—Ge three-center bond by hydrogen atoms contained in the microvoids is increased, Compensation and structural relaxation of dangling bonds of germanium atoms can be performed with a small hydrogen content.

The density of microvoids is set to 1 × 10
^By setting it to ¹⁹ (cm ⁻³ ) or less, unbonded hands (da
ngling bond) and film distortion can be further reduced.

Further, by setting the size and the number of the microvoids in the range of the present invention, the state of the interface when the non-single-crystal film is laminated can be improved.

In the non-single-crystal germanium semiconductor of the present invention, by setting the density of microvoids to 1 × 10 ¹⁹ (cm ⁻³ ) or less, the surface density of ^microvoids existing at the interface and the surface is set to 2 × 10 ⁺¹¹ (cm ³ ). cm ^-2 ) or less.

The average radius of the microvoids is 3.5 °.
Since the content is set to the following, the smoothness of the interface and the surface is improved. Therefore, when the non-single-crystal germanium semiconductor is stacked in the non-single-crystal germanium semiconductor of the present invention,
The interface state is reduced, and the interface strain is also reduced.

In addition, in the non-single-crystal germanium semiconductor of the present invention, the average radius of the microvoids is small and the density is small, so that the impurity doping efficiency is improved.

That is, since the average radius of the microvoids is small, the density of the microvoids is small, and the ratio of GeH ₂ bonds contained is small, the degree of freedom of the non-single-crystal germanium semiconductor is smaller than that of the conventional non-single-crystal semiconductor. Than has been reduced. As a result, when impurities are doped in the non-single-crystal germanium semiconductor of the present invention,
Impurities are reduced to 4 due to increased binding or reduced degrees of freedom.
The possibility of coordination in coordination increases, and the doping efficiency of impurities increases.

When silicon atoms are added to the non-single-crystal germanium semiconductor of the present invention to form a non-single-crystal silicon-germanium semiconductor, the bonding state between silicon atoms and hydrogen atoms is Si-H bond (2000 cm in IR spectrum).
^-1 peak) and SiH ₂ bond (2070 in IR spectrum)
～2100Cm ^-1 peak) and the area ratio (assuming a Gaussian distribution for each _{peak) [SiH 2] / [SiH} ] are those is preferably 1/20 or less.

The non-single-crystal germanium semiconductor of the present invention comprises:
It is suitable for application to photoreceptors for electrophotography, solar cells, thin film transistors, photoelectric conversion elements such as optical sensors, and semiconductor elements.

FIG. 1 is a schematic illustration of an electrophotographic light-receiving member to which the non-single-crystal germanium semiconductor of the present invention is applied. The electrophotographic light receiving member 104 includes a support 101.
It is configured by stacking a charge injection prevention layer 102 and a photoconductive layer 103 thereon.

The charge injection preventing layer 102 is formed by adding a Group IIIb element of the periodic table to the non-single-crystal germanium semiconductor of the present invention for positive charging and a Group Vb element of the periodic table for negative charging according to the present invention. Is desirably added to the non-single-crystal germanium semiconductor.

Further, for the charge injection preventing layer 102, a microcrystalline germanium semiconductor and a polycrystalline germanium semiconductor are particularly suitable among the non-single-crystal germanium semiconductors.

For the photoconductive layer 103, an amorphous germanium semiconductor is particularly suitable among non-single-crystal germanium semiconductors.

In addition, although the thickness of each layer should be appropriately determined by an electrophotographic process, the thickness of the charge injection preventing layer 102 is preferably 100 ° to 1 mm.
0 μm, more preferably 1000 ° to 7 μm, and most preferably 5000 ° to 5 μm. The layer thickness of the photoconductive layer 103 is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, and most preferably 10 μm to 4 μm.
0 μm.

When the non-single-crystal germanium semiconductor of the present invention is applied to an image forming member for electrophotography, the chargeability, the sensitivity, and the residual charge are substantially eliminated, the ghost is substantially eliminated, and the image flow is reduced. There is virtually no environmental resistance,
There are effects such as extremely stable image quality and long life.

In addition, the electrophotographic image forming member to which the non-single-crystal germanium semiconductor of the present invention is applied has an effect of high sensitivity especially when used in a laser beam printer using a semiconductor laser of infrared light. is there.

In addition, in the electrophotographic image forming member to which the non-single-crystal germanium semiconductor according to the present invention is applied, in order to improve the charging ability, the non-single-crystal silicon germanium obtained by adding an impurity to the charge injection preventing layer 102 is used. Semiconductors,
Non-single-crystal silicon semiconductors are preferred. Further, as the photoconductive layer, a function-separated type using a non-single-crystal silicon semiconductor for the charge transport layer and a non-single-crystal germanium semiconductor for the charge generation layer can be appropriately selected according to the electrophotographic process.

FIG. 2 is a schematic explanatory view of a solar cell to which the non-single-crystal germanium semiconductor of the present invention is applied. In FIG. 2, a solar cell 207 includes an n-type layer 202, an i-type layer 203, a p-type layer 204, and a transparent conductive layer 20 on a conductive support 201.
5 and the collecting electrode 206 are laminated.

Further, if necessary, a reflection layer or a reflection enhancement layer may be inserted between the conductive support 201 and the n-type layer 202. Further, in the case where the support is light-transmitting and light is irradiated from the support side, it is preferable to have an opposite layer configuration.

The n-type layer 202 and the p-type layer 204 are formed on the non-single-crystal germanium semiconductor of the present invention,
It is desirable to add a group b element and a group IIIb element of the periodic table. Further, among the non-single-crystal germanium semiconductors of the present invention, a microcrystalline germanium semiconductor or a polycrystalline germanium semiconductor is desirable. Further, the thickness of the n-type layer 202 and the p-type layer 204 is
、, more preferably 200Å to 10Å, and most preferably 100Å to 20Å.

In the case of a solar cell, the n-layer or the p-layer does not contribute to photocurrent even if it absorbs light. Therefore, it is desirable that the n-layer or the p-layer is as thin as possible.

The non-single-crystal germanium semiconductor of the present invention comprises:
When used as a thin film, a microvoid serving as an obstacle has a small average radius and a small density, so that a sufficient function can be exhibited even with a thin film of several tens of degrees.

As the i-layer, an amorphous germanium semiconductor or a polycrystalline germanium semiconductor among the non-single-crystal germanium semiconductors of the present invention is suitable. The thickness of the i-layer should be appropriately determined according to the light spectrum of the environment in which the solar cell is used, but is preferably 500 °
１1 μm.

As described above, when the non-single-crystal germanium semiconductor of the present invention is applied to a solar cell, the light absorption in the n-layer or the p-layer can be reduced, and the i-layer can sufficiently absorb light to perform photoelectric conversion. Is possible. In addition, since the non-single-crystal germanium semiconductor of the present invention has a small average diameter of microvoids and a small density, that is, is dense,
Diffusion of impurities in the n-layer and the p-layer into the i-layer is suppressed as much as possible, and an excellent pin junction can be formed.
Similarly, since the n layer or the p layer is dense, the metal of the transparent conductive layer (et. ITO, SnO ₂ ) can be prevented from diffusing into the n layer or the p layer. This is also one of the reasons why the n-layer or the p-layer using the non-single-crystal silicon semiconductor of the present invention exhibits sufficient characteristics with an extremely thin film.

Further, as a layer constitution of a solar cell to which the non-single-crystal germanium semiconductor of the present invention is applied, an n-layer or an n-layer for improving photovoltaic power, improving photocurrent, and improving form factor is provided. It is desirable that the p-layer be formed of a non-single-crystal silicon semiconductor or a non-single-crystal silicon germanium semiconductor having a wider bandgap than the i-layer. In particular, it is more desirable that the n-type or p-type layer on the light incident side is crystallized. This is because the crystallization reduces the light absorption coefficient and improves the conversion efficiency especially at short wavelengths.

In addition, the layer structure of the solar cell is such that a solar cell having a pin structure using a non-single-crystal silicon semiconductor as an i-layer and a solar cell having a pin structure using a non-single-crystal germanium semiconductor as an i-layer are stacked. A solar cell having a multilayer structure such as a tandem structure described above is a preferred example.

FIG. 3 is a schematic explanatory view of a thin film transistor to which the non-single-crystal germanium semiconductor of the present invention is applied. The thin film transistor 307 includes an insulating support 301.
Gate electrode 302, insulating layer 303, semiconductor layer 30
4, a source electrode 305 and a drain electrode 306 are laminated.

When the non-single-crystal germanium semiconductor of the present invention is applied to the semiconductor layer 304, the interface state between the semiconductor layer 304 and the insulating layer 303 is reduced, so that excellent transistor characteristics can be obtained. Further, stable transistor characteristics can be obtained even in repeated use.

FIG. 4 is a schematic explanatory view of an optical sensor to which the non-single-crystal germanium semiconductor of the present invention is applied. The optical sensor 406 includes an n-type or p-type layer 40 using a non-single-crystal germanium semiconductor of the present invention on a conductive support 401.
2. It is formed by laminating an i-type layer 403, a p- or n-type layer 404, and a transparent conductive layer 405 using the non-single-crystal germanium semiconductor of the present invention.

The optical sensor 406 has a pin structure, nip
All structures are used by applying a reverse bias. The desirable range of the reverse bias is 1 V to 10 V. The layer thickness of each layer of the optical sensor is the same as that of the solar cell, but in the case of the optical sensor, a reverse bias is applied, so that
It is desirable that the layer and the n-layer have a large layer thickness.

The optical sensor using the non-single-crystal germanium semiconductor of the present invention exhibits excellent effects such as low noise due to dark current, high sensitivity and no afterimage or deterioration.

In particular, in the optical sensor of the present invention, in order to reduce noise due to dark current when a reverse bias is applied, a non-single-crystal silicon semiconductor having a bandgap wider than the i-type layer as the n-type layer and the p-type layer is used. It is preferable to use a non-single crystal silicon germanium semiconductor.

Hereinafter, the method for forming a non-single-crystal germanium semiconductor according to the present invention will be described. As a method for forming a non-single-crystal germanium semiconductor of the present invention, a microwave glow discharge decomposition method using a germane source gas is suitable.

A source gas suitable for the glow discharge decomposition method and
And the following: In the present invention, a Ge atom
GeH is used as a source gas for supply._Four, Ge_TwoH₆, Ge_Three
H₈, Ge_FourH_Ten, Ge_FiveH₁₂, Ge₆H₁₄, Ge₇H₁₆,
Ge₈H₁₈, Ge₉H₂₀Such as germanium hydride and Ge
HF_Three, GeH_TwoF_Two, GeH_ThreeF, GeHCl_Three, GeH_Two
Cl_Two, GeH_ThreeCl, GeHBr_Three, GeH_TwoBr_Two, G
eH_ThreeBr , GeHl_Two, GeH_TwoI_Two, GeH_TwoWater such as I
Constituents of hydrogen atoms such as fluorinated germanium halides
Halide, GeF_Four, GeCl_Four, Ge
Br_Four, GeI_Four, GeF_Two, GeCl_Two, GeBr_Two, G
el_TwoSuch as germanium halides
Compounds.

Source for Si supply used in the present invention
The source gas is SiH_Four, Si_TwoH₆, Si_ThreeH₈, Si_Four
H_TenSilicon hydride in the gaseous state or gasifiable
Orchids) are mentioned as being effectively used,
In addition, the ease of handling the layer preparation work and the good Si supply efficiency
SiH in point , Si_TwoH₆Are preferred.
You.

As the raw material gas for introducing a halogen atom used in the present invention, many halogen compounds can be mentioned, for example, a gas state of a halogen gas, a halide, an interhalogen compound, a silane derivative substituted with halogen, or the like. Or halogenated compounds which can be gasified are preferred.

Further, in the present invention, a silicon compound containing a halogen atom, which is composed of a silicon atom and a halogen atom in a gaseous state or can be gasified, can be mentioned as an effective one.

Examples of the halogen compound that can be suitably used in the present invention include halogen gas of fluorine, chlorine, bromine and iodine, BrF, ClF, ClF ₃ and Br.
_{F 5, BrF 3, IF 3} , IF 7, ICl, may be mentioned interhalogen compounds such as IBr.

Examples of the silicon compound containing a halogen atom, ie, a silane derivative substituted with a halogen atom, include, for example, SiF ₄ , Si ₂ F ₆ , SiCl ₄ , SiBr
Silicon halides such as ₄ are preferred.

The above-described silicon compound containing a halogen atom may be employed and introduced into a deposition chamber characteristic of the present invention by a glow discharge method to form a plasma atmosphere of the gas.

In the present invention, the above-mentioned halogen compounds or halogen-containing silicon compounds are effectively used as the source gas for introducing halogen atoms, but HF, HCl, HBr, HI Hydrogen halides such as SiH ₂ F ₂ , SiH ₂ I ₂ , SiH ₂
Halogen-substituted silicon hydrides such as Cl ₂ , SiHCl ₃ , SiH ₂ Br ₂ , SiHBr ₃ , and other gaseous or gasifiable halides having a hydrogen atom as one of the constituent elements are also cited as effective starting materials. Can be.

These halides containing a hydrogen atom are:
In the present invention, a hydrogen atom which is extremely effective in controlling electric or photoelectric characteristics is introduced simultaneously with the introduction of a halogen atom into a layer formed at the time of layer formation. Is done.

When a glow discharge method is used to form a layer containing Group III atoms or Group V atoms, the starting material serving as a source gas for forming the layer is the same as the starting material for Si described above. A material appropriately selected from the above, to which a starting material for introducing a Group III atom or a Group V atom is added. As such a starting material for introducing a Group III atom or a Group V atom, a gaseous substance having a Group III atom or a Group V atom as a constituent atom or a gasified substance that can be gasified is used. , Any of them.

In the present invention, a substance effectively used as a starting material for introducing a group III atom, specifically, for introducing a boron atom, may be B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ ,
_{B 5 H 11, B 6 H} 10, B 6 H 12, B 6 H 14 borohydride such as,
Examples thereof include boron halides such as BF ₃ , BCl ₃ , and BBr _{3. In} addition, AlCl ₃ , GaCl ₃ , and I
nCl ₃ , TlCl _{3 and the} like can also be mentioned.

In the present invention, effectively used as a starting material for introducing a Group V atom is, specifically, for introducing a phosphorus atom, a hydrogenated phosphorus such as PH ₃ or P ₂ H ₄ or a PH ₄ I,
PF ₃ , PF ₅ , PCl ₃ , PCl ₅ , PBr ₃ , PBr ₅ ,
Phosphorus halides such as PI ₃ ; In addition, As
H ₃ , AsF ₃ , AsCl ₃ , AsBr ₃ , AsF ₅ , Sb
H ₃ , SbF ₃ , SbF ₅ , SbCl ₃ , SbCl ₅ , Bi
H ₃ , BiCl ₃ , BiBr _{3 and the} like can also be mentioned.

Furthermore, deuterium is mentioned as a source gas that plays an important role in forming the non-single-crystal germanium semiconductor of the present invention. The preferred ratio of deuterium for forming the non-single-crystal germanium semiconductor of the present invention is 0.5 to 100 with respect to the germanium feed gas.

Deuterium gas is activated by microwave energy and emits ultraviolet rays. The radiation intensity of ultraviolet rays is stronger with deuterium gas than with hydrogen gas. Therefore, when a non-single-crystal germanium semiconductor is formed by a microwave glow discharge decomposition method by adding deuterium gas to a germanium-based source gas, the microwave of the present invention is irradiated with ultraviolet rays emitted from deuterium excited by microwaves. The average particle size of the voids is 3.5 mm or less and the density is 1
A non-single-crystal germanium semiconductor having a size of × 10 ¹⁹ cm ⁻³ or less can be formed.

That is, the germane source gas in the gas phase is activated by ultraviolet rays emitted from deuterium excited by microwaves to generate active species. The active species are considered to be more suitable for forming the non-single-crystal germanium semiconductor of the present invention than the active species generated by microwave glow discharge decomposition of a source gas containing no deuterium.

The ultraviolet rays emitted from the deuterium also activate and promote the surface reaction on the support, and it is considered that the non-single-crystal germanium semiconductor of the present invention is obtained.

Further, since deuterium has a larger atomic weight than hydrogen, it is considered that photodeterioration related to hydrogen taken into the non-single-crystal germanium semiconductor is reduced.

The conditions of the microwave glow discharge decomposition method for forming a non-single-crystal germanium semiconductor of the present invention are as follows. That is, the frequency of the microwave is preferably 100 MHz to 10 GHz, and optimally 2.
It is 45 GHz.

Further, a DC bias and R
It is necessary to superimpose the F bias. The DC bias is preferably applied such that the support side becomes negative, and the optimal DC bias is 10 to 200 V.

Further, the preferable frequency of the RF bias is 5
00KHz to 50MHz, optimally 13.56M
Hz. The optimum range of the power of the RF bias is 5 × 10 ^{−2 to} 400 W / sc with respect to the silicon-based source gas.
cm.

DC bias and R are applied to microwave glow discharge.
By superimposing the F bias, the surface reaction on the surface of the support when the silicon-based source gas is decomposed and deposited can be promoted, and the damage due to the collision of electrons on the film formation surface of the support can be reduced. The RF bias is effective in preventing abnormal discharge based on the shape of the reaction vessel.

Further, in the microwave glow discharge decomposition method for forming a non-single-crystal silicon semiconductor according to the present invention,
The pressure during glow discharge decomposition is a very important factor, and the optimal range is 0.1 to 10 mTorr. Further, the power of the microwave is also an important factor, and the optimum power for the silicon-based source gas is 1 to 10 W / sccm.

In addition, the temperature of the support during film formation is an important factor related to the film quality of the non-single-crystal germanium semiconductor.
It should be determined appropriately depending on the deposition rate and the desired non-single-crystal germanium semiconductor (crystalline or amorphous).
In the case where the deposition rate is as low as several Å or less and an amorphous germanium semiconductor is formed, the temperature of the support should be set relatively low, and a preferable range is 25 to 400 ° C.

In the case where the deposition rate is as low as several Å or less and a crystalline germanium semiconductor is formed, the temperature of the support is preferably set to be relatively high.
６００600 ° C. When a non-single-crystal germanium semiconductor is deposited at a deposition rate of several tens of degrees or more and at a high rate, the temperature of the support is preferably set to be relatively high, and a preferable range is 250 to 650 ° C.

[0089]

EXPERIMENTAL EXAMPLES Hereinafter, the present invention will be described in more detail by way of experimental examples, but the present invention is not limited thereto.

[0090]

EXPERIMENTAL EXAMPLE 1 A sample for measuring impurity doping efficiency, a sample for microvoid analysis, and crystallinity using the non-single-crystal germane semiconductor of the present invention by a microwave (hereinafter abbreviated as “μW”) glow discharge decomposition method. An analysis sample was prepared.

FIG. 5 shows an apparatus for producing a non-single-crystal germane semiconductor by a μW glow discharge decomposition method comprising a source gas supply device 520 and a film formation device 500.

In the gas cylinders 571 to 575 in the figure,
A source gas for manufacturing the non-single-crystal germane semiconductor of the present invention is sealed, and 571 is a SiH ₄ gas (purity 9).
(9.99%) cylinder and 572 are deuterium gas (purity 99.99%).
6%, hereinafter abbreviated as “D ₂ gas”. 573 is a PH ₃ gas (purity 99.9) diluted to 10% with H ₂ gas.
99%, hereinafter abbreviated as “PH ₃ / H ₂ (10%) gas”) P or diluted to 10 ppm with a cylinder or H ₂ gas
H ₃ gas (99.999% purity, hereinafter referred to as “PH ₃ / H ₂ (1
0 ppm) gas.) The cylinder 574 is a B ₂ H ₆ gas (purity 99.999) diluted to 10% with H ₂ gas.
%, Hereinafter abbreviated as “B ₂ H ₆ / H ₂ (10%) gas”)
Cylinder or diluted to 10ppm with H ₂ gas B ₂ H ₆ gas (99.999% purity, hereinafter _{"B 2 H 6 / H 2 (} 10p
pm) gas), 575 is GeH
₄ (purity: 99.999%). When the gas cylinders 571 to 575 are attached to the raw material gas supply device 520 in advance, the respective gases are introduced from the valves 551 to 555 into the gas pipes of the inflow valves 531 to 535, and the respective gas pressures are adjusted by the pressure regulators 561 to 565. 2 kg / cm ²
Has been adjusted to. Further, gas cylinders 573 and 574
Can be adjusted to PH ₃ / H ₂ (10%) or PH ₃ / H ₂ (10 ppm) and B ₂ H ₆ / H ₂ (10
%) Or B ₂ H ₆ / H ₂ (10 ppm).

In the drawing, reference numeral 504 denotes a support, which is 50 mm square.
It is made of stainless steel (SUS304) having a thickness of 1 mm, is mirror-finished on its surface, and is electron beam evaporated with chromium (Cr) metal to a thickness of 0.1 μm.

First, the valves 551 to 555 are opened, and then it is confirmed that the inflow valves 531 to 535 and the leak valve 509 of the film forming chamber 501 are closed.
After confirming that the outflow valves 541 to 545 and the auxiliary valve 508 are opened, the conductance (butterfly type) valve 507 is fully opened, and the inside of the film forming chamber 501 and the gas pipe is exhausted by a vacuum pump (not shown). Vacuum gauge 50
When the reading of No. 6 became about 1 × 10 ⁻⁴ Torr, the auxiliary valve 508 and the outflow valves 541 to 545 were closed.

Next, the inflow valves 531 to 535 are gradually opened, and each gas is supplied to the mass flow controller 521.
~ 525. After the preparation for film formation was completed as described above, a film of a non-single-crystal germane semiconductor was formed on the support 504.

In order to produce a non-single crystal germane semiconductor,
The support 504 is heated to 350 ° C. by the heater 505.
Heating, outflow valves 541, 542, 545, auxiliary valve
508 and, if necessary, the outflow valves 543 and 544
Open each, SiH_FourGas, D_TwoGas, GeH_FourGas and
PH as required_Three/ H_Two(10%) gas, PH_Three/ H
_Two(10 ppm) gas, B _TwoH₆/ H_Two(10%) gas and
B _TwoH₆/ H_Two(10 ppm) gas into the gas inlet tube 503
Through this, it flowed into the film forming chamber 501. At this time, SiH _Four
Gas flow rate 3 sccm, D_TwoGas flow rate is 100scc
m, GeH_FourGas flow rate 2 sccm, PH_Three/ H_Two(10
%) Gas flow rate, PH_Three/ H_Two(10 ppm) gas flow rate, B
_TwoH₆/ H_Two(10%) gas flow rate and B _TwoH₆/ H_Two(10p
pm) Each gas flow rate was set so that the gas flow rate was as shown in Table 1.
It was adjusted by the sflow controllers 521 to 525. Success
The pressure in the film chamber 501 is vacuumed so as to be 2 mTorr.
Opening of conductance valve 507 while looking at total 506
Was adjusted. Next, the DC power supply 511 controls the film forming chamber 50.
A DC bias of -90 V to 1 and an RF power supply
513, 0.8 mW / cm^ThreeRF power, high frequency
Mark the support 504 through the wave matching box 512
Added. Then, the power of the μW power supply (not shown) is
W / cm^ThreeAnd the waveguide (not shown), the waveguide 51
0 and the dielectric window 502 into the film formation chamber 501 in μW.
A force is applied to generate a μW glow discharge,
Production of a non-single crystal germane semiconductor was started on the
When a non-single-crystal germane semiconductor of m
The low discharge is stopped, and the DC power supply 511 and the RF power supply 513 are stopped.
Turn off the output, and output valves 541-545 and auxiliary
By closing the valve 508, the gas flow into the film formation chamber 501 is stopped.
The fabrication of the non-single crystal germane semiconductor was completed.

Next, on the surface of the non-single crystal germane semiconductor,
Chromium (Cr) metal having a diameter of 2 mm and a thickness of 0.1 μm as the upper electrode is deposited by electron beam evaporation, and is doped with a small amount of impurities, a small amount of impurities, and a large amount of impurities. A sample for measurement was produced (Sample No. Ex. 1-1 to 1-1)
9).

Table 2 shows the conditions for preparing the above-mentioned sample for measuring the doping efficiency of impurities.

Next, a non-single-crystal germane semiconductor was placed on a high-purity aluminum foil of 5 mm square and 10 μm thick under the same manufacturing conditions as those of the sample for measuring the effect of impurity doping.
A sample for microvoid analysis was prepared by forming a film having a thickness of μm.

On a 5 mm square, 1 mm thick stainless steel support, a non-single-crystal germane semiconductor was formed in a thickness of 3 μm under the same manufacturing conditions to prepare a sample for microvoid and crystallinity analysis.

[0101]

Comparative Example 1 A sample for measuring impurity doping efficiency using a conventional non-single-crystal germane semiconductor by a high frequency (hereinafter abbreviated as “RF”) glow discharge decomposition method.
A sample for microvoid analysis and a sample for crystallinity analysis were prepared.

FIG. 6 shows an apparatus for producing a non-single-crystal germane semiconductor by RF glow discharge decomposition comprising a source gas supply apparatus 620 and a film forming apparatus 600.

In the gas cylinders 671-675 in the figure,
A source gas for manufacturing a conventional non-single crystal germane semiconductor is sealed, and 672 is H ₂ gas (purity 99.9).
999%) except that the gas cylinder is the same as the source gas supply device 520 of Experimental Example 1. in advance,
As in Experimental Example 1, each gas was introduced into a gas pipe,
By adjusting each gas pressure, gas cylinders 673 and 674 are
Replace as needed for experiment. In the figure, reference numeral 604 denotes Experimental Example 1
The same support as described above.

First, the same operation procedure as in Experimental Example 1 was used.
After each gas was introduced into the mass flow controllers 621 to 625 to complete preparation for film formation, a non-single-crystal germane semiconductor film was formed on the support 604.

To produce a non-single crystal germane semiconductor,
The support 604 is heated to 250 ° C. by the heater 605.
Heating, outflow valve 641, 642, 645, auxiliary valve
608 and, if necessary, the outflow valves 643 to 644
Open each, SiH_FourGas, H _TwoGas, GeH_FourGas and
PH as required_Three/ H_Two(10%) gas, PH_Three/ H
_Two(10 ppm) gas, B _TwoH₆/ H_Two(10%) gas and
B _TwoH₆/ H_Two(10 ppm) gas into the gas inlet tube 603
Through this, it flowed into the film forming chamber 601. At this time, SiH _Four
Gas flow rate 0.6 sccm, H_TwoGas flow rate 50scc
m, GeH_FourGas flow rate 0.4 sccm, PH_Three/ H
_Two(10%) gas flow rate, PH_Three/ H_Two(10 ppm) gas
Flow rate, B _TwoH₆/ H_Two(10%) gas flow rate and B _TwoH₆/
H_Two(10ppm) The gas flow rate is the value shown in Table 3.
With each mass flow controller 621-625
It was adjusted. The pressure in the film forming chamber 601 becomes 1 Torr
The conductance valve 6 while looking at the vacuum gauge 606.
07 opening was adjusted. Then, the power of the RF power supply 613
5 mW / cm^ThreeSet to high frequency matching box
RF power is introduced to cathode 602 through 612 and R
F glow discharge is generated, and a non-single crystal
Production of Le Mans semiconductor was started, and non-single-crystal
Stop RF glow discharge after manufacturing Le Mans semiconductor
Outflow valves 641-645 and auxiliary valve 608
Close and stop the gas flow into the film formation chamber 601,
The fabrication of the Germanic semiconductor has been completed.

Next, on the surface of the non-single crystal germane semiconductor,
The upper electrode was vapor-deposited in the same manner as in Experimental Example 1 to produce a sample for measuring the impurity doping efficiency similar to that in Experimental Example 1 (sample No. ratio 1-1 to 9). Table 4 shows the manufacturing conditions for the above-described sample for measuring the doping efficiency of impurities.

Next, a non-single-crystal germane semiconductor was placed on a 5-mm square high-purity aluminum foil having a thickness of 10 μm under the same manufacturing conditions as the sample for measuring the doping efficiency of impurities.
A sample for microvoid analysis was prepared by forming a film having a thickness of μm.

On a 5 mm square, 1 mm thick stainless steel support, a non-single crystal germane semiconductor was formed to a thickness of 3 μm under the same manufacturing conditions to prepare a sample for microvoid and crystallinity analysis.

Experimental Example 1 (Sample Nos. Examples 1-1 to 9)
And a sample for measuring the doping efficiency of the impurity prepared in Comparative Experimental Example 1 (sample No. ratio 1-1 to 9) was used as a cryostat (WM-365, manufactured by Sanwa Radio Surveying Instruments Laboratory).
And using a pA meter (4140B, manufactured by Yokogawa Hewlett-Packard Co., Ltd.) to apply a voltage between the upper electrode and the stainless steel support, and measure the temperature of the sample for measuring the doping efficiency of impurities (T: absolute temperature). ), The current (Id) flowing between both electrodes is measured, and the natural logarithm of the current (log.Id) with respect to the reciprocal of temperature (1 / T) is measured.
The activation energy of the non-single-crystal germane semiconductor was determined by multiplying the slope of -8.6 × 10 ^-5 .

As a result, when no impurity was doped, the activation of the non-single-crystal germane semiconductors in Experimental Example 1 (Sample No. 1-5) and Comparative Experimental Example 1 (Sample No. ratio 1-5) was performed. Energy was about the same value. However, when a small amount of impurity was doped, the non-single-crystal germane semiconductor of Comparative Experimental Example 1 (Sample Nos. 1-3, 4, 6, and 7) was compared with Experimental Example 1 (Sample N).
The non-single-crystal germane semiconductors of Examples 1-3, 4, 6, and 7) have a change ratio of the activation energy of 1.9 to 2.4.
In the case of doping with a large amount of impurities and a large amount of impurities, the non-single-crystal germane semiconductor of Comparative Example 1 (sample No. ratio 1-1, 2, 8, and 9) was compared with Experimental Example 1 (sample No. The activation energy values of the non-single-crystal germane semiconductors of 1-1, 2, 8, and 9) are 0.4 to 0.6.
The sample for measuring the doping efficiency of impurities using the non-single-crystal germane semiconductor of the present invention (sample No.
Actually, the activation energies are significantly different from those of the conventional non-single-crystal germane semiconductor for impurity doping efficiency measurement samples (sample Nos. Ratios 1-1 to 9) of Comparative Experimental Example. Therefore, it was found that the composition had excellent doping efficiency, and the effect of the present invention was proved.

Then, 3 μm of non-single-crystal germane semiconductor was placed on a high-purity aluminum foil of 5 mm square and 10 μm thick.
The average radius and density of the microvoids in the non-single-crystal germane semiconductor were measured using a small-angle X-ray scattering device (RAD-IIIb type, manufactured by Rigaku Denki) for the microvoid analysis sample having the m film thickness. As a result, in the non-single-crystal germane semiconductor of Experimental Example 1, the average radius of the microvoids was 2.7 to 2.0.
At 9 °, the density is 5.6 to 8.3 × 10 ¹⁸ (cm ⁻³ ), and the non-single-crystal germane semiconductor of Comparative Experimental Example 1 has an average microvoid radius of 3.8 to 4.0 °, The density is 2.
0 to 3.1 × 10 ¹⁹ (cm ⁻³ ), and the non-single-crystal germane semiconductor of Experimental Example 1 has a smaller average diameter of microvoids and a lower density than the non-single-crystal germanic semiconductor of Comparative Experimental Example 1. It turned out to be small.

A microvoid having a non-single-crystal germane semiconductor film thickness of 3 μm and a sample for crystallinity analysis were formed on a 5 mm square, 1 mm thick stainless steel support by STM (NANO manufactured by Digital Instrument).
SVOPE-II) was used to observe microvoids on the surface of the non-single-crystal germane semiconductor. As a result, the non-single-crystal germane semiconductor of Experimental Example 1 had a smaller radius and a smaller number of microvoids than the non-single-crystal germane semiconductor of Comparative Experimental Example 1. Next, RHEED (manufactured by JEOL)
When the crystallinity of the non-single-crystal germane semiconductor was evaluated by JEM-100SX), Experimental Example 1 and Comparative Experimental Example 1 were evaluated.
A ring-shaped pattern was observed in each sample.
It was found to be amorphous (including microcrystals).

[0113]

EXPERIMENTAL EXAMPLE 2 A non-single-crystal germanium semiconductor device comprising a p-type layer, an i-type layer and an n-type layer using the non-single-crystal germane semiconductor of the present invention was used as a production apparatus shown in FIG. Thus, it was manufactured under the same manufacturing conditions as in Experimental Example 1. The support 504 is made of stainless steel (SUS304) having a size of 50 mm square and a thickness of 1 mm, and its surface is mirror-finished.

To form the p-type layer, the support 504 is added.
Heated to 350 ° C. with a heat heater 505,
By the same operation, SiH_Four3 sccm of gas, D_Twogas
100 sccm, GeH_Four2 sccm of gas, B _TwoH₆
/ H_Two(10%) 5 sccm gas in the film forming chamber 501
And adjust the pressure in the deposition chamber 501 to 2mTorr
did. Next, the DC bias was set to -90 V, and the RF power was set to 0.
8mW / cm^Three, ΜW power of 60 mW / cm^ThreeUnder the condition
By the same operation as in Experimental Example 1, the layer thickness 1 was formed on the support 504.
A 0 nm p-type layer was produced.

Next, to form an i-type layer, the support 50
4 was heated to 350 ° C. by the heater 505, and the same operation as in Experimental Example 1 was performed to supply SiH ₄ gas at 3 sccm.
100 sccm of D ₂ gas, ₂ sccm of GeH ₄ gas,
It is allowed to flow into the film forming chamber 501 and the pressure in the film forming chamber 501 is set to 2
Adjusted to mTorr. Next, the DC bias is set to -90.
V, RF power 0.8 mW / cm ³ , μW power 60 m
Under the conditions of W / cm ³ , p
An i-type layer having a thickness of 500 nm was formed on the mold layer.

Next, to form an n-type layer, the support 50
4 was heated to 350 ° C. by the heater 505, and the same operation as in Experimental Example 1 was performed to supply SiH ₄ gas at 3 sccm.
100 sccm of D ₂ gas, ₂ sccm of GeH ₄ gas,
PH ₃ / H ₂ (10%) was introduced into the film forming chamber 501 at 5 sccm, and the pressure in the film forming chamber 501 was adjusted to 2 mTorr. Next, the DC bias was set to -90 V, and the RF power was set to 0.
8mW / cm ^3, the μW power under the conditions of 60mW / cm ^3,
By the same operation as in Experimental Example 1, a layer thickness of 10 nm was formed on the i-type layer.
Was produced.

When forming the respective layers, it goes without saying that the outflow valves 541 to 545 other than the necessary gas are completely closed. From 541 to 545, the film forming chamber 50
In order to avoid remaining in the piping leading to 1, the outflow valves 541 to 545 are closed, the auxiliary valve 508 is opened,
Further, the conductance valve 507 is fully opened, and an operation of once evacuating the system to a high vacuum is performed as necessary.

The n of the manufactured non-single crystal germane semiconductor device
ITO (In ₂ O ₃ + Sn) as a transparent conductive layer on the mold layer
O ₂ ) was deposited in a size of 6 mm in diameter and 70 nm in thickness by a resistance heating method to produce a non-single-crystal germane semiconductor element (element No. 2). Table 5 shows the manufacturing conditions of the non-single-crystal germane semiconductor element.

[0119]

COMPARATIVE EXPERIMENT 2 A non-single-crystal germanium semiconductor element comprising a p-type layer, an i-type layer and an n-type layer using a conventional non-single-crystal germane semiconductor was manufactured as shown in FIG. The device was manufactured under the same manufacturing conditions as in Comparative Experimental Example 1 using an apparatus. The support was made of a 50 mm square, 1 mm thick stainless steel (SUS30
4) was used.

To form a p-type layer, the support 604 is added.
Heated to 250 ° C by a heat heater 605, a comparative example
By the same operation as in Step 1,_Four0.6 scc of gas
m, H_Two50 sccm gas, GeH_Four0.4 sc gas
cm, B _TwoH₆/ H_Two(10%) 1 sccm gas deposition
Flow into the chamber 601 and the pressure in the film forming chamber 601 is set to 1 To
rr. Next, the RF power was set to 5 mW / cm^ThreeArticle
In this regard, by the same operation as in Comparative Experimental Example 1, the support
A p-type layer having a thickness of 10 nm was formed thereon.

Next, to prepare an i-type layer, the support 60
4 was heated to 250 ° C. by the heater 605, and the same operation as in Comparative Experimental Example 1 was performed to reduce the SiH ₄ gas for 0.6 s.
ccm, H ₂ gas 50 sccm, a GeH ₄ gas 0.4
The flow rate of sccm was introduced into the film forming chamber 601, and the pressure in the film forming chamber 601 was adjusted to 1 Torr. Next, increase the RF power by 5 m
Under the conditions of W / cm ³ , an i-type layer having a thickness of 500 nm was formed on the p-type layer by the same operation as in Comparative Experimental Example 1.

Next, to form the n-type layer, the support 60
4 was heated to 250 ° C. by the heater 605, and the same operation as in Comparative Experimental Example 1 was performed to reduce the SiH ₄ gas for 0.6 s.
ccm, H ₂ gas 50 sccm, a GeH ₄ gas 0.4
sccm, PH ₃ / H ₂ (10%) was introduced into the film formation chamber 601 at a flow rate of 1 sccm, and the pressure in the film formation chamber 601 was set at 1 Torr.
adjusted to r. Next, an n-type layer having a thickness of 10 nm was formed on the i-type layer by the same operation as in Comparative Experimental Example 1 under the condition of RF power of 5 mW / cm ³ .

When forming each layer, it goes without saying that the outflow valves 641 to 645 other than the necessary gas are completely closed. From 641 to 645, the film forming chamber 60
In order to avoid remaining in the pipe leading to 1, the operation of once evacuating the system to a high vacuum is performed as necessary by the same operation as in Experimental Example 2.

The n of the manufactured non-single crystal germane semiconductor device
A transparent conductive layer was vapor-deposited on the mold layer in the same manner as in Experimental Example 2 to produce a non-single-crystal germane semiconductor element (element number ratio 2). Table 6 shows the manufacturing conditions of the non-single-crystal germane semiconductor element.

The non-single-crystal germane semiconductor elements produced in Experimental Example 2 (element No. 2) and Comparative Example 2 (element No. ratio 2) were measured with a pA meter (4140B manufactured by Yokogawa Hewlett-Packard Co., Ltd.). By applying a voltage between the transparent conductive layer and the support made of stainless steel and measuring current-voltage characteristics, the Physics of Sem was used.
icon Devices (2nd Ed
ition S. M. Sze JOHN WILEY
& SONS) on pages 89 to 92, the n value of the pn junction was determined. As compared with the comparative experimental example 2 (element No. ratio 2), the experimental example 2 (element No. actual 2)
The n-value of the non-single-crystal germanium semiconductor element is 0.79 times as small as that of the non-single-crystal germanium semiconductor of the present invention. It turned out to be obtained.

Next, phosphorus (P) atoms and i-type layers in the i-type layer of the non-single-crystal germanium semiconductor devices manufactured in Experimental Example 2 (Element No. Ex. 2) and Comparative Experimental Example 2 (Element No. 2) The content of boron (B) atoms was measured using a secondary ion mass spectrometer (CAM).
When analyzed by IMS-3F manufactured by ECA, the non-single-crystal germanium semiconductor device of Experimental Example 2 (Device No. Ex. 2) was compared with Comparative Experimental Example 2 (Device No. Ratio 2) by phosphorus (P) atom. Is 0.8 times and the content of boron (B) atoms is as small as 0.3 times, and the diffusion of impurities is better when the non-single-crystal germanium semiconductor of the present invention is used than in the conventional non-single-crystal germane semiconductor. It turned out to be difficult.

[0127]

[Experimental Example 3] Experimental example 2 except that an n-type layer, an i-type layer, a p-type layer, and a transparent conductive layer were formed in this order on a stainless steel support, and the thickness of the i-type layer was 3 µm. A non-single-crystal germane semiconductor device was manufactured under the same manufacturing conditions as in (Device N
o. Actual 3).

[0128]

Comparative Example 3 An n-type layer, i
A non-single-crystal germane semiconductor device was manufactured under the same manufacturing conditions as in Comparative Example 2 except that a layer was formed in the order of a mold layer, a p-type layer, and a transparent conductive layer, and the layer thickness of the i-type layer was 3 μm. (Element No. ratio 3).

Experimental Example 2 (Element No. Ex. 2), Experimental Example 3
(Element No. Actual 3), Comparative Experimental Example 2 (Element No. Ratio 2)
And the mobility of electrons and holes in the non-single-crystal germane semiconductor of the non-single-crystal germane semiconductor device manufactured in Comparative Experimental Example 3 (element No. ratio 3) was measured by SEMICONDUCT.
ORS AND SEMIMETALS VOLUME
21 PartC CHAPTER6 (T.Tiedj
e) According to the time-of-flight method described in ACADEMIC PRESS, the comparative example 2 (element No. ratio 2) was compared with the experimental example 2 (element No. 2).
The non-single-crystal germane semiconductor device of Ex. 2) has a hole mobility as large as 3.3 times, which is larger than that of Comparative Ex. 3 (Ex. 3). In the non-single-crystal germane semiconductor element, the mobility of electrons is as large as 1.7 times, and it has been found that the non-single-crystal germane semiconductor of the present invention is easier to transfer charges than the conventional non-single-crystal germane semiconductor. .

[0130]

EXPERIMENTAL EXAMPLE 4 A non-single-crystal germane semiconductor device was manufactured under the same manufacturing conditions as in Experimental Example 2 except that the thicknesses of the p-type layer and the n-type layer were each set to 2 nm (element No. Ex. 4).

[0131]

Comparative Experimental Example 4 A non-single-crystal Germanic semiconductor device was manufactured under the same manufacturing conditions as in Comparative Experimental Example 2 except that the thickness of each of the p-type layer and the n-type layer was 2 nm (element No. ratio 4). ).

Fabricated in Experimental Example 2 (Device No. 2), Experimental Example 4 (Device No. 4), Comparative Experimental Example 2 (Device No. Ratio 2) and Comparative Experimental Example 4 (Device No. Ratio 4). Using a pA meter (4140B manufactured by Yokogawa Hewlett-Packard Co., Ltd.) to apply a voltage between the transparent conductive layer and the stainless steel support to measure the current-voltage characteristics of the non-single-crystal germane semiconductor element The leakage current at the reverse bias voltage was measured according to the following formula. As a result, the non-single-crystal germanium semiconductor device of Experimental Example 2 (Device No. Actual 2) exhibited a leak current of Comparative Example 2 (Device No. Ratio 2). 0.42
The non-single-crystal germanium semiconductor device of Experimental Example 4 (Device No. 4) has a leak current as small as 0.07 times that of Comparative Example 4 (Device No. Ratio 4). It has been found that the use of the non-single-crystal germane semiconductor of the present invention allows a thin film to be more sufficiently used than the non-single-crystal germane semiconductor.

[0133]

[Experimental Example 5 and Comparative Experimental Example 5] 5 mm square and 10 μm thick
1mm thick 5mm square stainless steel foil
On a stainless steel (SUS304) support, D_TwoGas flow or
H_TwoThe gas flow rate was changed to the value shown in Table 7 and the operation shown in Table 8 was performed.
Depending on the manufacturing conditions, a micro-bo
And a sample for crystallinity analysis were prepared (Sample N
o. Samples 5-1 to 3-1 and sample Nos. Ratio 5). Furthermore, 5
On a 0 mm square, 1 mm thick stainless steel support, i-type
Layer D_TwoGas flow rate or H_TwoChange the gas flow rate to the value shown in Table 7
In the same manner as in Experimental Example 2 under the manufacturing conditions shown in Table 9,
A non-single crystal germane semiconductor device was fabricated by the
o. Examples 5-1 to 3 and element Nos. Ratio 5).

The prepared microvoids and samples for crystallinity analysis (Sample Nos. 5-1 to 3 and Sample N
o. The ratio 5) was measured by measuring the average radius and density of the microvoids using a small-angle X-ray scattering device in the same manner as in Experimental Example 1.
By D, the crystallinity of the non-single-crystal germane semiconductor was measured. The results are shown in FIG. Further, the fabricated non-single-crystal germane semiconductor elements (element Nos. 5-1 to 3 and element No. ratio 5) were connected to a pn junction n in the same manner as in Experimental Examples 2 to 4.
The value, the mobility of holes in a non-single-crystal germane semiconductor, and the leakage current at a reverse bias voltage were measured. The results of the above measurements are also shown in FIG. 7 as relative values, where the value of the non-single-crystal germane semiconductor device of Comparative Experimental Example 5 (device No. ratio 5) is 1. As can be seen from FIG. 7, the microvoids of the present invention have an average radius of 3.5 ° or less and a density of 1 × 10 ¹⁹ (c
m ^-3 ) or less of a non-single-crystal germane semiconductor device (device No.
Examples 5-1 to 3) show excellent characteristics in any of the n value, the hole mobility, and the leak current as compared with the conventional non-single-crystal germane semiconductor element (element No. ratio 5). The effect has been demonstrated.

[0135]

[Experimental example 6] High-purity aluminum foil of 5 mm square and 10 μm thickness
Top and 5mm square, 1mm thick stainless steel (SUS3
04) On the support, Experiments were performed under the manufacturing conditions shown in Table 10.
For microvoid and crystallinity analysis in the same manner as in Example 1.
A sample was prepared (Sample No. Ex. 6). Furthermore, 5
Table 1 was placed on a 0 mm square, 1 mm thick stainless steel support.
According to the manufacturing conditions shown in FIG.
A single-crystal germane semiconductor device was fabricated (device No.
6).

[0136]

[Comparative Experimental Example 6] High-purity aluminum 5 mm square and 10 μm thick
1mm thick stainless steel (SU
S304) On the support, According to the manufacturing conditions shown in Table 12,
Microvoids and crystals were obtained in the same manner as in Comparative Experimental Example 1.
A sample for sex analysis was prepared (sample No. ratio 6).
Furthermore, on a 50 mm square, 1 mm thick stainless steel support
In the same manner as in Comparative Experimental Example 2 under the manufacturing conditions shown in Table 13,
A non-single-crystal germane semiconductor device was fabricated by a simple method.
Child No. Ratio 6).

The microvoid analysis samples (sample No. 6 and sample No. ratio 6) prepared were measured for the average radius and density of the microvoids using a small-angle X-ray scattering apparatus in the same manner as in Experimental Example 1. As a result, the non-single-crystal germane semiconductor of Experimental Example 6 had an average radius of microvoids of 3.2 ° and a density of 9.1 × 10 ¹⁸ (cm ⁻³ ),
The non-single-crystal germane semiconductor of Comparative Experimental Example 6 had an average radius of microvoids of 3.9 ° and a density of 2.2 × 10
^{It was 19} (cm ⁻³ ), and it was found that the non-single-crystal germane semiconductor of Experimental Example 6 had a smaller average radius of microvoids and a lower density than the non-single-crystal germanic semiconductor of Comparative Experimental Example 6.

The crystallinity of the non-single-crystal germane semiconductor was evaluated by RHEED for the prepared samples for crystallinity analysis (sample No. 6 and sample No. ratio 6) in the same manner as in Experimental Example 1. In each of the samples of Comparative Example 6 and Comparative Example 6, a ring-shaped pattern was observed, it was observed that the sample was amorphous (including microcrystals), and it was found that the sample was amorphous (including microcrystals). .

Further, the fabricated non-single-crystal germane semiconductor element (element No. 6 and element No. ratio 6) was fabricated in Experimental Example 5.
Similarly to the above, the n value of the pn junction, the mobility of holes in the non-single-crystal germane semiconductor, and the leak current at the reverse bias voltage were measured. As a result, the n-value of the pn junction of the non-single-crystal germane semiconductor device of the experimental example 6 (element No. 6) was higher than that of the non-single-crystal germane semiconductor device of the comparative experimental example 6 (element No. ratio 6). The hole mobility was 0.78 times smaller, the hole mobility was 2.5 times larger, and the leak current was 0.15 times smaller. In each case, excellent characteristics were exhibited, demonstrating the effect of the present invention.

[0140]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

[0141]

Example 1 A 50 mm square, 1 mm thick stainless steel (S
U.S. Pat. No. 304), a silver thin film of 0.1 μm as a reflection layer and a ZnO thin film of 1 μm as a reflection enhancement layer were formed on a conductive support having a mirror-finished surface by sputtering.
m was deposited. An n-type layer, an i-type layer, and the like were formed on the conductive support by the same operation as in Experimental Example 2 under the production conditions shown in Table 14.
Films were formed in the order of the p-type layer, and ITO was deposited on the p-type layer as a transparent conductive layer in a size of 1 cm square and 70 nm thick in the same manner as in Experimental Example 2, and further collected on the transparent conductive layer. As an electrode, a solar cell was fabricated by electron beam evaporation of aluminum (Al) metal to a thickness of 2 μm (solar cell No. 1).

[0142]

[Comparative Example 1] Under the same conditions as in Example 1 except that an n-type layer, an i-type layer, and a p-type layer were manufactured by the same operation as in Comparative Experimental Example 2 under the manufacturing conditions shown in Table 15, A battery was manufactured (solar cell No. ratio 1).

The initial characteristics and the deterioration characteristics of the solar cells manufactured in Example 1 (solar cell No. 1) and Comparative Example 1 (solar cell No. ratio 1) were evaluated.

The initial characteristics are shown in Example 1 (Battery No. 1)
The solar cell manufactured in Comparative Example 1 (battery No. ratio 1) was placed under irradiation with AM-1.5 (100 mW / cm ² ) light, and the photoelectric conversion efficiency was measured and evaluated. As a result of the characteristic evaluation, Example 1 was compared with Comparative Example 1 (battery No. ratio 1).
The solar cell of (Battery No. Ex. 1) has a photoelectric conversion efficiency of 1.
31 times better.

The deterioration characteristics are shown in Example 1 (battery No. 1).
And the solar cell manufactured in Comparative Example 1 (battery No. ratio 1) was irradiated with AM-1.5 (100 mW / cm ² ) light.
After being left for 00 hours, A
M-1.5 (100 mW / cm ² ) installed under light irradiation,
The photoelectric conversion efficiency was measured and evaluated. As a result of the characteristic evaluation, Example 1 (Battery N) was compared with Comparative Example 1 (Battery No. ratio 1).
o. Actually, the solar cell of 1) was superior in photoelectric conversion efficiency by 1.6 times.

From the above results, it has been found that the solar cell using the non-single-crystal germane semiconductor of the present invention has excellent solar cell characteristics.

[0147]

Example 2 A 50 mm square, 1 mm thick stainless steel (S
U.S. Pat. No. 304) and a mirror-finished conductive support on an n-type layer, i under the same manufacturing conditions as in Example 1.
A layer was formed in the order of a mold layer and a p-type layer. On the p-type layer, as a transparent conductive layer, ITO was vapor-deposited in a size of 2.5 mm in diameter and 100 nm in thickness in the same manner as in Example 1 to form an optical sensor. It was produced (Sensor No. Ex. 2).

[0148]

Comparative Example 2 An optical sensor was manufactured under the same conditions as in Example 2 except that an n-type layer, an i-type layer, and a p-type layer were manufactured under the same manufacturing conditions as in Comparative Example 1 (sensor No. ratio). 2).

The optical sensors prepared in Example 2 (sensor No. 2) and Comparative Example 2 (sensor No. ratio 2)
An oscilloscope (Sony Tektronix Co., Ltd.) measures the rise and fall of the current flowing between the conductive support and the transparent conductive layer by intermittently irradiating the light of the red light emitting diode.
, Model 2430) was used to evaluate the light responsiveness. As a result, with respect to Comparative Example 2 (sensor No. ratio 2), the optical sensor of Example 2 (sensor No. actual 2)
The light response was 2.7 times better.

From the above results, it has been found that the optical sensor using the non-single-crystal germane semiconductor of the present invention has excellent optical sensor characteristics.

[0151]

Example 3 A gate electrode was formed on a 50 mm square, 0.8 mm thick insulating support made of barium borosilicate glass (7059, manufactured by Corning Incorporated) as a gate electrode, 16 μm wide and 10 mm long.
Chromium (Cr) metal having a size of 0 μm and a thickness of 100 nm is electron-beam evaporated, and an insulating layer is formed on the gate electrode.
Silicon nitride having a width of 50 μm, a length of 100 μm, and a thickness of 500 nm is deposited by a glow discharge decomposition method.
A non-single-crystal germanium semiconductor layer having a thickness of 0 μm, a length of 100 μm, and a thickness of 500 nm was formed under the same manufacturing conditions as the i-type layer of Example 1, and a source electrode and a drain electrode were formed on the non-single-crystal germane semiconductor layer. Width 10μm, length 100
Chromium (Cr) metal having a thickness of 100 μm and a thickness of 100 nm was subjected to electron beam evaporation at a distance of 10 μm between the source electrode and the drain electrode, thereby producing a thin film transistor (T).
FT No. Actual 3).

[0152]

Comparative Example 3 A thin film transistor was manufactured under the same conditions as in Example 3 except that a non-single-crystal germane semiconductor layer was manufactured under the same manufacturing conditions as the i-type layer of Comparative Example 1.
No. Ratio 3).

A pA meter (4140B, manufactured by Yokogawa Hewlett Packard KK) was connected to the thin film transistors fabricated in Example 3 (TFT No. 3) and Comparative Example 3 (TFT No. 2), and a gate electrode was formed. The current flowing between the drain electrode and the source electrode when a voltage was applied between the drain electrode and the source electrode was measured, and the on-current and the on-off current ratio were evaluated. As a result, Comparative Example 3 (TFT No.
Compared to the ratio 3), the thin film transistor of Example 3 (TFT No. 3) was 3.7 times better in on-current and 5.1 times better in on-off current ratio.

From the above results, it was found that the thin film transistor to which the non-single-crystal germane semiconductor of the present invention was applied had excellent thin film transistor characteristics.

[0155]

Example 4 A photoreceptor for electrophotography using the non-single-crystal germane semiconductor of the present invention was produced by the μW glow discharge decomposition method.

FIGS. 8A and 8B show the raw material gas supply device 8.
20 shows an apparatus for producing a photoreceptor for electrophotography by a μW glow discharge decomposition method, comprising an apparatus 20 and a film forming apparatus 800.

In the gas cylinders 871 to 874 in the figure,
A source gas for producing the electrophotographic light-receiving member of the present invention is sealed, and 871 is a SiH ₄ gas (purity 9).
(9.99%) cylinder, 872 is D ₂ gas (purity 99.6)
%) Cylinder, 873 is B ₂ H diluted to 1% with H ₂ gas
₆ gases (purity 99.999%, hereinafter referred to as “B ₂ H ₆ / H ₂ (1
%) ") And 874 are GeH ₄ gas (99.999% purity) cylinders. Each gas is introduced into the gas pipe in advance and the pressure of each gas is adjusted in the same manner as in Experimental Example 1. In the figure, reference numeral 807 denotes a cylindrical support made of aluminum having a diameter of 108 mm, a length of 358 mm, and a thickness of 5 mm and having a mirror-finished surface.

First, as in Experimental Example 1, each gas was introduced into the mass flow controllers 821 to 824. After the preparation for film formation was completed as described above, a light receiving member for electrophotography comprising a charge injection preventing layer and a photoconductive layer was formed on the support 807.

To form the charge injection preventing layer, the support 8
07 heated to 300 ° C by a heater (not shown)
And the outflow valves 841 to 843 and the auxiliary valve 808
Open gradually, SiH_FourGas, D_TwoGas and B_TwoH₆/ H_Two
(1%) gas is supplied to a gas discharge hole (not shown) of a gas introduction pipe 810.
) Into the plasma generation space 809.
At this time, SiH_FourGas flow rate 200 sccm, D_TwoGas flow
Amount is 1000sccm, B_TwoH₆/ H_Two(1%) gas flow
Control each mass flow control so that
Roller 821-823. Pressure in the deposition chamber 801
Apply a vacuum gauge (not shown) so that the force becomes 1 mTorr.
Adjust the conductance valve (not shown) while watching
It was adjusted. Next, a DC power supply 811 is used to enter the film forming chamber 801.
A DC bias of -120 V is applied to the
According to 13, 40 mW / cm^Three RF power
Apply to the support 807 through the switching box 812
Was. Thereafter, the power of the μW power supply (not shown) is increased by 800 mW.
/ Cm^ThreeAnd the waveguide (not shown), the waveguide 803
And into the plasma generation chamber 809 through the dielectric window 802
μW power is introduced to generate μW glow discharge,
The formation of the charge injection preventing layer was started on
When the charge injection prevention layer of
Stop and cut off the output of DC power supply 811 and RF power supply 813
Outflow valves 841 to 843 and the auxiliary valve 8
08, the gas flow into the film formation chamber 801 is stopped,
The fabrication of the anti-loading layer was completed.

Next, in order to form a photoconductive layer, the support 8
07 is heated to 300 ° C. by a heater (not shown), and the outflow valves 841, 842, and 844 are gradually opened, and SiH ₄ gas, D ₂ gas, and GeH ₄ gas are discharged from the gas discharge holes ( (Not shown) into the plasma generation space 809. At this time, the SiH ₄ gas flow rate was 130 sccm, the D ₂ gas flow rate was 1200 sccm,
The mass flow controllers 821, 822, and 824 adjusted the GeH ₄ gas flow rate to 70 sccm. The opening of the conductance valve (not shown) was adjusted while watching the vacuum gauge (not shown) so that the pressure in the film forming chamber 801 became 1 mTorr. Next, the DC power supply 81
1, a DC bias of −80 V was applied to the film forming chamber 801, and an RF power of 50 mW / cm ³ was applied to the support 807 through the high frequency matching box 812 by the RF power supply 813. Thereafter, the power of a μW power supply (not shown) is set to 700 mW / cm ³ , and μW power is introduced into the plasma generation chamber 809 through a waveguide (not shown), a waveguide 803 and a dielectric window 802. , A glow discharge is caused to start producing a photoconductive layer on the charge injection preventing layer, and when a photoconductive layer having a thickness of 25 μm is produced,
W glow discharge is stopped, DC power supply 811 and RF power supply 81
3 and the outflow valves 841, 842, 8
44 and the auxiliary valve 808 were closed to stop the gas flow into the film formation chamber 801, and the fabrication of the photoconductive layer was completed.

In forming each layer, it goes without saying that the outflow valves 841 to 844 other than the necessary gas are completely closed. From 841 to 844, the film forming chamber 80
In order to avoid remaining in the pipe leading to 1, the outflow valves 841 to 844 are closed, the auxiliary valve 808 is opened,
Further, an operation of fully opening a conductance valve (not shown) and once evacuating the system to a high vacuum is performed as necessary. Table 16 shows the conditions for producing the electrophotographic light-receiving member.
(Drum No. 4).

[0162]

Comparative Example 4 A D ₂ gas cylinder was charged with H ₂ gas (purity 99.99).
(99%) The same manufacturing apparatus as in Example 4 was used except that the cylinder was replaced.
In the same manner as described above, a light-receiving member for electrophotography was manufactured using a conventional non-single-crystal germane semiconductor (drum N).
o. Ratio 4).

The light receiving member for electrophotography (drum No. 4 and ratio 4) produced in Example 4 and Comparative Example 4 was installed in a Canon copier NP-9330 modified for experiment.
The charging ability, sensitivity, temperature characteristics, optical memory, and uniformity of the electrophotographic light-receiving member were evaluated by the methods described below.

The charging ability was evaluated by measuring the dark area potential under certain charging conditions. The sensitivity was evaluated by adjusting the charging conditions so as to obtain the same dark portion potential, and then measuring the difference between the bright portion potential and the dark portion potential when a constant amount of light was irradiated.

The temperature characteristics were evaluated by measuring the change rate of the dark area potential when the temperature of the electrophotographic light receiving member was 25 ° C. and 44 ° C. After irradiating a part of the electrophotographic light receiving member with 1500 lux fluorescent lamp light for 12 hours, a halftone image is copied, and the part irradiated with the fluorescent lamp light and the part not irradiated with the light are used. Evaluation was made by measuring the image density difference.

The uniformity was evaluated by measuring the image density at 100 points in a halftone image with a circular area having a diameter of 0.05 mm as one unit in order to measure the degree of roughness. As a result of the above evaluation,
The conventional electrophotographic light receiving member of Comparative Example 4 (Drum No.
In contrast to the ratio 4), the electrophotographic light-receiving member of the present invention (drum No. 4) of Example 4 has a charging ability 1.2 times larger, a sensitivity 1.2 times better, and a temperature characteristic (dark area). Potential change rate) (0.45 times), optical memory (image density difference)
Is as low as 0.55 times and uniformity (variation in image density)
Was as small as 0.6 times, and was excellent in all evaluation items.

As an image evaluation, when a character generator prepared for an experiment was used to visually evaluate the image quality evaluation of the formed image, the conventional light receiving member for electrophotography of Comparative Example 4 (drum No. ratio) was used. On the other hand, the light receiving member for electrophotography (drum No. 4) of the present invention of Example 4 has a fine character with little tangling and an image of good resolution with a clear boundary between black and white. And
In addition, even if the entire image is viewed, there is little unevenness in density, fog, roughness, etc., halftone is sufficiently reproduced, uniformity is sufficiently excellent, it is a very good image, and image quality is excellent There was found.

A non-single-crystal germane semiconductor was formed in a thickness of 3 μm on a 5 mm square high-purity aluminum foil having a thickness of 10 μm under the same manufacturing conditions as the photoconductive layer of Example 4 and Comparative Example 4, and the microvoid analysis was performed. Sample (photoconductive layer sample No. 4 and ratio 4), and the average radius and density of microvoids were measured by a small-angle X-ray scattering apparatus in the same manner as in Experimental Example 1. The average radius of the microvoids of the germane semiconductor (photoconductive layer sample No. 4) was 3.1 °, the density was 6.5 × 10 ¹⁸ (cm ⁻³ ), and the non-single-crystal germane semiconductor of Comparative Example 4 ( The average radius of the microvoids in the photoconductive layer sample No. ratio 4) was 3.9 °, and the density was 1.7 × 10 ¹⁹ (cm ⁻³ ).

From the above evaluation results, the microvoids of the present invention have an average radius of 3.5 ° or less and a density of 1 × 10 ^19.
It was found that a light-receiving member for electrophotography to which a non-single-crystal germane semiconductor of (cm ^-3 ) or less was applied had excellent electrophotographic characteristics.

[0170]

[Table 1]

[0171]

[Table 2]

[0172]

[Table 3]

[0173]

[Table 4]

[0174]

[Table 5]

[0175]

[Table 6]

[0176]

[Table 7]

[0177]

[Table 8]

[0178]

[Table 9]

[0179]

[Table 10]

[0180]

[Table 11]

[0181]

[Table 12]

[0182]

[Table 13]

[0183]

[Table 14]

[0184]

[Table 15]

[0185]

[Table 16]

[0186]

[Table 17]

[0187]

The non-single-crystal germanium semiconductor of the present invention has a large load mobility and a long life. Moreover, it is hard to deteriorate by light. Further, there is an effect that doping efficiency when impurities are added is high, and diffusion of impurities is difficult. In addition, the non-single-crystal germanium semiconductor of the present invention is a semiconductor suitable for application to photoelectric conversion elements and semiconductor elements such as solar cells, optical sensors, thin film transistors, and electrophotographic image forming members.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram for explaining a layer configuration of an electrophotographic light-receiving member to which a non-single-crystal germane semiconductor of the present invention is applied.

FIG. 2 is a schematic configuration diagram illustrating a layer configuration of a solar cell to which the non-single-crystal germane semiconductor of the present invention is applied.

FIG. 3 is a schematic configuration diagram for explaining a layer configuration of a thin film transistor to which the non-single-crystal germane semiconductor of the present invention is applied.

FIG. 4 is a schematic configuration diagram for explaining a layer configuration of an optical sensor to which the non-single-crystal germane semiconductor of the present invention is applied.

FIG. 5 is a schematic explanatory view of an example of an apparatus for producing a non-single-crystal germane semiconductor of the present invention, which is a production apparatus based on a glow discharge method using μW.

FIG. 6 is a schematic explanatory view of an example of a conventional apparatus for manufacturing a non-single-crystal germane semiconductor, which is a manufacturing apparatus based on a glow discharge method using RF.

FIG. 7 shows the average radius, density, and crystallinity of microvoids of the present invention and the conventional non-single-crystal germanium semiconductor, the hole mobility of the non-single-crystal germane semiconductor, the n value of the non-single-crystal germane semiconductor device, and the leakage current. It is explanatory drawing which shows a relationship.

FIG. 8 is a schematic explanatory view of an example of an apparatus for producing a photoreceptor for electrophotography using the present invention and a conventional non-single-crystal germane semiconductor, which is manufactured by a glow discharge method using μW.

FIG. 9 is a schematic explanatory view of an example of an apparatus for producing an electrophotographic light-receiving member to which the present invention and a conventional non-single-crystal germane semiconductor are applied, which are manufactured by a glow discharge method using μW.

[Explanation of symbols]

Reference Signs List 101 support 102 charge injection preventing layer 103 photoconductive layer 104 electrophotographic light receiving member 201 conductive support 202 n-type layer 203 i-type layer 204 p-type layer 205 transparent conductive layer 206 current collecting electrode 207 solar cell 301 insulation Support 302 gate electrode 303 insulating layer 304 semiconductor layer 305 source electrode 306 drain electrode 307 thin film transistor 401 conductive support 402 n-type or p-type layer 403 i-type layer 404 p-type or n-type layer 405 transparent conductive layer 406 Optical sensor 500 μW Film forming apparatus by glow discharge decomposition method 501,601,801 Film forming chamber 502,802 Dielectric window 503,603 Gas introduction tube 504,604 Support 505,605 Heater 506,606 Vacuum gauge 507,607 Conductance valves 508, 608, 08 Auxiliary valve 509, 609 Leak valve 510 Waveguide 511, 811 DC power supply 512, 612, 812 High frequency matching box 513, 613, 813 RF power supply 520, 620, 820 Source gas supply device 521-525, 621-625, 821 -824 Mass flow controller 531-535,631-635,831-834 Gas inflow valve 541-545,641-645,841-844 Gas outflow valve 551-555,651-655,851-854 Valve of raw material gas cylinder 561-565 , 661-665, 861-864 Pressure regulators 571-575, 671-675, 871-874 Source gas cylinder 600 Film forming apparatus by RF glow discharge decomposition method 602 Cathode 800 gW glow discharge decomposition method Film forming apparatus 803 waveguide 807 support 809 plasma generating space 810 gas introduction pipe electrophotographic light-receiving member that.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tatsuyuki Aoike 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Mitsuyuki Niwa 3-30-2 Shimomaruko, Ota-ku, Tokyo (56) References JP-A-4-318980 (JP, A) JP-A-4-268721 (JP, A) Non-Crystalline Solids 114 (1989) p226-228 (58) Fields investigated (Int. Cl. ⁶ , DB name) H01L 21/20 JICST file (JOIS)

Claims (3)

(57) [Claims] 1. A non-single-crystal germanium semiconductor containing at least germanium atoms and hydrogen atoms and / or halogen atoms, wherein the microvoids present in the semiconductor film have an average radius of 3.5 ° or less and a density of 1 × 10 ^19. (C
m- ³ ) Non-single-crystal germanium semiconductor characterized by the following. 2. The non-single-crystal germanium semiconductor according to claim 1, wherein the non-single-crystal germanium semiconductor contains silicon atoms. 3. The non-single-crystal germanium semiconductor according to claim 1, wherein the non-single-crystal germanium semiconductor contains a group IIIb element and / or a group Vb element of the periodic table.