JPH02379A - P-i-n type photovoltaic device - Google Patents

Abstract

PURPOSE:To obtain a photovoltaic device having high photoelectric conversion efficiency by composing at least the I-type semiconductor layer of the photovoltaic device by the junctions of a P-type semiconductor layer, the I-type semiconductor layer and an N-type semiconductor of zinc atom, selenium atoms and at least hydrogen atoms. CONSTITUTION:An electrode 102, an N-type semiconductor layer 103, an I-type semiconductor layer 104, a P-type semiconductor layer 105, a transparent electrode 106 and a collecting electrode 107 are formed onto a supporter 101 in the order, thus shaping a photovoltaic device 100. At least the I-type semiconductor layer in these semiconductor layers consists of zinc atoms, selenium atoms and at least hydrogen atoms, the hydrogen atoms are contained in 1-4atomic% quantity, and the I-type semiconductor layer is constituted of a deposit film in which the rate of crystal grains per unit volume is brought to 65-85vol.%. Accordingly, photoelectric conversion efficiency having efficiency particularly higher to short wavelength light than a photovoltaic device using P-I-N junctions is acquired.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical field to which the invention pertains] The present invention relates to an improved photovoltaic device suitable as a power source for consumer equipment and a solar cell for electric power. More specifically, the present invention relates to the photovoltaic element using a pin junction and having high photoelectric conversion efficiency, particularly for short wavelength light.

[Description of Prior Art] Conventionally, silicon (Si) and gallium arsenide (GaAs) have been used as power supplies for consumer devices, photovoltaic elements such as solar cells, etc.
Photovoltaic devices have been proposed that utilize pin junctions, which are formed by ion implantation or thermal diffusion of impurities into single crystal substrates, such as, or by epitaxial growth of layers doped with impurities on such single crystal substrates. There is.

However, since these devices use single-crystal substrates as described above, their manufacturing costs are extremely high, and it is difficult to reduce them. The reality is that it has not yet become widespread.

By the way, in recent years, glass, metal,
Amorphous silicon (hereinafter referred to as r
A photovoltaic device using a pin junction formed by forming a deposited film (called A-SiJ) has been proposed, and because it is reasonably satisfactory and low cost, it is widely used in calculators, wristwatches, etc. It has been used as a power source for a limited number of consumer devices.

However, such photovoltaic devices have a low output voltage because the bandgap of the A-Silli that makes up the photovoltaic device is around 1.7 eV, which is not sufficiently large. There is a problem in that sufficient photoelectric conversion efficiency cannot be obtained for a light source with a large proportion of wavelength light. For this reason, application to consumer devices is limited to devices with extremely low power consumption.
-3i films often have a property called the so-called 5taebler-Wronski effect, in which charging characteristics deteriorate when continuously irradiated with strong light.For this reason, the above-mentioned photovoltaic elements are stable over long periods of time. This is not of practical use as a power solar cell that is required to maintain such characteristics.

In particular, when designing solar cells for power generation using photovoltaic elements, it is important to effectively convert sunlight into electricity, and in particular convert sunlight with a wide spectral distribution into as wide a wavelength range as possible It is important to have a layer structure that allows photoelectric conversion.

Incidentally, when a photovoltaic element is formed using a semiconductor material with a small energy band gap, the wavelength range of light absorbed by the film expands over a wide range from the short wavelength side to the long wavelength side. Since the amount of energy extracted is determined by the energy bandgap of the semiconductor material used, the long wavelength component only contributes to photoelectric conversion, and the energy of the short wavelength light component is not effectively used for charging conversion.

On the other hand, when a photovoltaic element is formed using a semiconductor material with a large energy bandgap, the wavelength component of sunlight that is absorbed by the film and contributes to photoelectric conversion has energy greater than the energy bandgap of the semiconductor material used. The short wavelength light component and the long wavelength light component are not charged and converted.

In addition, the maximum voltage taken out to the outside as a photovoltaic element, that is, the open circuit voltage (Voc) is determined by the energy band gap value of the semiconductor material to be bonded, and a high voltage
A semiconductor material with a large band gap is effective in obtaining oc.

Therefore, even if a photovoltaic element is formed using only one semiconductor material and an attempt is made to perform the desired photoelectric conversion as a solar cell, there is naturally a limit to the photoelectric conversion efficiency.

For this reason, a plurality of photovoltaic elements are formed using a plurality of semiconductor materials having different energy band gaps, and wavelengths to be photoelectrically converted by the photovoltaic elements formed of semiconductor materials having each energy band gap. There is a proposal for a method to improve the photoelectric conversion efficiency of sunlight by dividing the area.

However, since the layer structure of the solar cell proposed in this proposal is a so-called electrically series structure in which a plurality of photovoltaic elements are stacked, the characteristics of the individual photovoltaic elements are good (
Otherwise, high photoelectric conversion efficiency cannot be obtained as a whole.

Then, a high Voc with a large band gap is obtained,
In addition, the actual situation is that a photovoltaic element having sufficient characteristics as a photovoltaic element on the light incident side when a plurality of the above-mentioned photovoltaic elements are stacked has not yet been realized.

On the other hand, as a direct transition semiconductor with a wide bandgap, Z
n5e (band gap: 2.67aV) and ZnT
e (bandgap -2.2BeV) or their mixed crystal ZnSel-XTex
(However, 0<x<1) has been proposed and evaluated.

However, such direct transition semiconductor films are generally obtained by epitaxial growth on single crystal substrates, and as-grown films are made of, for example, Zn5.
e indicates an n-type conductivity type, and ZnTe indicates a p-type conductivity type, but it is considered difficult to control both to the opposite conductivity type. Furthermore, epitaxial growth requires the use of expensive single crystal substrates, high substrate temperatures, and slow deposition rates.
It is impossible to use materials with low heat resistance such as inexpensive glass or synthetic resins as substrates, and there are many problems in terms of practical application. The membrane becomes extremely limited in its uses. However, although attempts have been made to deposit the above-mentioned direct transition semiconductor films on non-single crystal substrates such as glass, metals, ceramics, and synthetic resins, the resulting deposited films have various defects in them. As a result, a thin film with good electrical properties cannot be obtained.
Therefore, it is extremely difficult to control the conductivity type by doping, and it is difficult to obtain a thin film with good electrical characteristics.

By the way, amorphous (
Suggestions regarding amorphous (amorphous) films can be found in the known literature. These documents include U.S. Pat. No. 4,217.
No. 374 (hereinafter referred to as "Document 1"), US Pat. Regarding z'nSe compounds, there are JP-A-61-189649 (hereinafter referred to as "Document 3") and JP-A-61-189650 (hereinafter referred to as "Document 4"). .

However, Document 1 describes the use of selenium (Se), or even terel (Te), zinc (Zn), hydrogen (H), and lithium (
Although it mentions an amorphous semiconductor film containing Ll), the main component is an amorphous Se semiconductor film or an amorphous Te semiconductor film, and Zn contains Li,
Zn and LL are just additives on the same level as H, and are used to reduce the local level density in the energy gap without changing the inherent properties of the film. It states that.

In short, the addition of Zn to amorphous Se or amorphous Te in Document 1 actively
However, Document 1 is not intended to form Zn5e compounds, ZnTe compounds, Zn5
There is no mention of the formation of el-, Ta, compounds, Zn5e crystal grains, ZnTe crystal grains, Zn5e,-, Te, crystal grains. Furthermore, regarding the addition of Li, it is not added as a dopant.

Although Document 2 describes an amorphous semiconductor film containing Se or further Te%Zn and H, the main content of Document 2 is related to amorphous 'xSi, and Ss and Te are not included. It is described as forming a compound, and Zn is said to be an element for sensitizing photoconductivity and for reducing the local level density in the energy gap of an amorphous semiconductor film.

That is, the addition of Zn, Se and Te results in a Zn5e compound,
ZnTe compound, Zn S e I+x' T e
, not for forming a compound. Incidentally, in document 2,
Zn5e compound, ZnTe compound, ZnS e,
-IITe, compound/substance, znSe crystal grain, Z n' T
There is no mention of the formation of e grains or ZnS e l-w Tam grains.

Documents 3 and 4 are based on the HR-CVD method () lydrogen Radlcal As5lst.
The content of this document is to dramatically improve the productivity of the film by increasing the film deposition rate when depositing Zn5ell using the ed CVD Method, and does not merely disclose a deposited film composed of non-doped Zn5e. ing.

Against this background, there is a particular need for inexpensive photovoltaic elements that can achieve high charging conversion efficiency for short wavelength light and can be put to practical use not only as power sources for consumer devices but also as solar cells for electric power. Early provision is a social demand.

[Object of the Invention] The present invention solves the above-mentioned conventional problems related to photovoltaic devices used in devices such as solar cells, and provides a suitable photovoltaic device that satisfies the above-mentioned social demands. The purpose is to

That is, an object of the present invention is to provide a photovoltaic element that uses a pin junction, can obtain high photoelectric conversion efficiency particularly for short wavelength light, and can be suitably used in equipment such as solar cells. Our goal is to provide the following.

The object of the present invention is to use glass, metal, and
Functional deposits that can form good pin-to-pin connections even when deposited on substrates made of inexpensive materials such as ceramics and synthetic resins, and even on certain types of films formed on such substrates. The object of the present invention is to provide a photovoltaic element that can be suitably used in devices such as solar cells using membranes.

[Configuration and Effects of the Invention] The present inventors first used the present invention to create a photovoltaic element for a solar cell or the like. Zn5e film and bandgap 2.2
In order to overcome the conventional problems with ZnS, el-IITe, and films of ev~2.4ev, and to further achieve the above-mentioned purpose of the present invention, we have conducted extensive research to develop Zn5e films and Zn5
For e+-xTexli, deposited films containing a specific amount of hydrogen atoms and controlling the ratio of crystal grains per unit volume to a predetermined value (i.e., Zn5e: HH and Zn5et-, Tax: Hll) were created. , the deposited film is deposited in a desired state on the surface of the substrate, such as glass, metal, ceramics, synthetic resin, etc., and the Zn5e:H1li and the Zn5e+-,T
e1l: H film has extremely few defects in the film, can introduce a p-type dopant into a desired state, has high doping efficiency, and is a non-single film with good p-type conductivity. The knowledge that yields a crystalline film was obtained from the experimental results presented below. Of course, the non-single-crystalline film according to the present invention can also be used as an n-type conductive film with high doping efficiency and good film strength and characteristics.

Based on this knowledge, the present inventors conducted further research, and found that the non-single-crystalline film has excellent properties, and when the film is used in a pin junction device, the device This work was completed after obtaining the knowledge to generate the desired photovoltaic force.

However, the gist of the present invention lies in the following photovoltaic device. That is, (1) a photovoltaic element that generates photovoltaic force by junction of a p-type semiconductor layer, an l-type semiconductor layer, and an n-type semiconductor layer, in which at least the l-type semiconductor layer among the semiconductor layers is A deposited film composed of zinc atoms, selenium atoms, and at least hydrogen atoms, in which the hydrogen atoms are contained in an amount of 1 to 4 atomic%, and the ratio of crystal grains per unit volume is 65 to 85% by volume. (2) a p-type semiconductor layer and/or an n-type semiconductor layer as well as the l-type semiconductor layer are composed of zinc atoms, selenium atoms, and at least hydrogen atoms; The deposited film contains a p-type or n-type doping agent, contains hydrogen atoms in an amount of 1 to 4 atoIIic%, and has a crystal grain ratio of 65 to 85% by volume per unit volume. pin type photovoltaic device,
(3) The p-type doping agent is Group 1 or V of the periodic table.
and (4) a pin-type photovoltaic device in which the p-type doping agent is a lithium atom. (5) A photovoltaic element that generates photovoltaic force by joining a p-type conductor layer, an l-type semiconductor layer, and an n-type semiconductor layer, in which at least the l-type semiconductor layer is , is composed of a zinc atom, a selenium atom, a tellurium atom, and at least a hydrogen atom, wherein the quantitative ratio of the selenium atom to the tellurium atom is in the range of 1:9 to 3:7 in terms of atomic ratio, and the hydrogen atom is 1 to 3:7. 4 atomic%, and the ratio of crystal grains per unit volume is 65 to 85.
(6) A pin-type photovoltaic device comprising a deposited film having a volume of It is composed of an atom, a tellurium atom, and at least a hydrogen atom, and contains a p-type or n-type doping agent, and the quantitative ratio of the selenium atom to the tellurium atom is in the range of 1:9 to 3:7 in terms of atomic ratio. and the hydrogen atoms are 1 to 4
atomic%, and the ratio of crystal grains per unit volume is 65 to 85% by volume. and (8) a pin photovoltaic device whose p-type doping agent is a lithium atom.

The above-mentioned experiments conducted by the present inventors will be described in detail below.

[Experiment] Uncut sword (11th section) Mouth!1 (i) As a substrate, thickness 0.5t+*, 11nc
hφ size circular low resistance (resistivity ρ-10-IΩcm
2. The wafer was thermally oxidized in a 02 gas flow at 1000° C. to form about 5000 S i 02 tll on a p-type St single crystal univer of 2. A quartz glass substrate with a size of 5 cm square was prepared.

(it) Next, the above two types of substrates are simultaneously set in parallel at predetermined positions of the substrate holder 202 of the known device shown in FIG.
e: Htli was formed to prepare samples Nos. 1 to 1271 and samples Nos. 1' to 12'.

Table 1 (+ii) Then, sample No. 1 to 1 on Si wafer
Cut 2 in half, and place each cut into 5 pieces to fit into the holder of a TEM (transmission electron microscope).
Cut into a size of Ilffi angle, and place the cut piece with the deposited film side in contact with the surface of a glass plate of size 50 mm x 50 mm with a thickness of 1 + nm so that the part on the deposited film side can be seen from the other side of the glass plate. Fixed using wax.

(iV) Then, a mixed solution of H'F, HNO3, CH3C0OH and water, in which the concentration of HF was adjusted with water, was prepared, and the sample prepared in (ii) was mixed with The exposed portion of the St-single crystal wafer was etched using the mixed solution. At that time, the etching rate was controlled by changing the concentration of HF in the mixed solution.

The etching process was completed when a portion of the Si-single crystal wafer was completely etched away by applying light from the deposited film side and observing the state of the transmitted light.

(V) After etching the sample, the wax was dissolved away using an organic solvent (toluene), the deposited film was removed from the glass plate, washed with water and air-dried.
A test sample consisting of Zn5e:Ha on i was obtained.

(2) Measurement of the test conducted in (1) above Sample Nos. 1 to 12 on the Sl wafer prepared in (1) above
Each test sample was subjected to TEM (acceleration voltage: 200k
eV) to form a transmission image,
I made that observation. The obtained transmission image contains Zn5e:Hl
A lattice image with very little lattice disorder was observed where a crystal grain region existed in ll. Furthermore, this lattice image is Z
n5e: uniformly distributed in all parts of Hllii.

Based on the lattice image, measure how many crystal grain regions are present per certain area of the test sample, and calculate the ratio of crystal grain regions in the deposited film in volume % (Vol, %). Calculated and evaluated.

At this time, for confirmation, the orientation of the crystal grains and the size of the crystal grain region were measured using X-ray diffraction, and these measurement results were also referred to.

(Measurement of the amount of H in 31III (1) (1) - (+1) Cut the samples No. 1' to 12' prepared on the quartz substrate in half, and put each sample in a vacuum chamber. , 1000℃ from room temperature
The amount of hydrogen atoms (H) released from the sample was determined using a mass spectrometer. As a standard sample, a sample was used in which a predetermined amount of H was ion-implanted into a sample prepared under conditions that did not contain any H.

(100) Also, sample No. 1 to 1 for TEM111 observation
2, the distribution state and elemental composition of Zn atoms and Se atoms in the deposited film were analyzed for each sample using an X-ray microanalyzer (manufactured by Shimadzu Corporation, hereinafter abbreviated as "XMA"). . The measurement results were as shown in Table 2.

Judging from the above measurement results, for all samples No. 1 to 12, Zn atoms and Se atoms are uniformly distributed in the deposited film, and the composition ratio of Zn atoms and Se atoms;
It was found that the ratio of Se was approximately 1:1 and satisfied the stoichiometric relationship.

Table 2 (4) Gai Yu The measurement results in (2) and (3) above are summarized in FIG. From the results shown in Figure 5, Zn5e:Hll
As the content (atomic%) of hydrogen atoms (H) in l increases, the ratio of crystal grain area per unit volume in the film decreases, and the hydrogen atom content in the film decreases to 0, 1 at.
It has been found that in the range of omic% to 10 atomic%, the ratio of grain regions in the film per unit volume is in the range of 90% to 40% by volume.

In addition, in preparing the sample in (1) above, if the H gas flow rate is set to 0.05 sec or less, the deposited film formed will be a film composed mostly of Zn, and the H gas flow rate will be 0.05 sec or less.
When the flow rate of the two gases was 251 m or more, no deposited film was formed.

For each of the remaining half samples No. 1' to 12' that were formed on the quartz substrate in A-(1)-(th) above, interdigitated All electrodes were deposited and the dark conductivity of the film was measured. The results are summarized in Figure 6. From the results in Figure 6, AMI irradiation light 1 question with electrical conductivity a is 0. , the ratio of the value σ after 8 hours is Δσ雛σ/σ. The rate of change in dark conductivity in terms of
) was found to increase rapidly from 8 atomic%, and it was also found that at 4 atomic% or less, there was almost no change in properties due to light irradiation.

Next, in A-(1)-(14), Sl-
The sto. formed on the wafer. The remaining half of sample No. 1~
For each of 12, a translucent film of AIL was deposited,
AIL-5 While a pulse voltage that makes A1 negative is applied between the i-wafers, a light pulse of UV light of about 1 n5 ec is irradiated and the drift mobility of holes is measured using the time-off flight method. When we measured the 7th
The dependence results shown in the figure were obtained.

From the results shown in Figure 7, it can be seen that the hydrogen atom content in the film is 0,
It was found that the hole drift mobility is an extremely small value below 5 ato+*ic%, and a large value is obtained when the hydrogen atom content in the film is in the range of 1 stomic% to 8 atoa+lc%. It was also found that when the hydrogen atom content in the film was 8 atomic % or more, the value of drift mobility decreased, albeit gradually.

From the above results, the hydrogen atom content in the film is 8 atomic % or less, preferably 4 atomic % or less, from the viewpoint of property changes due to light irradiation, and from the viewpoint of hole mobility, it is 0.5 atomic % or less. atomic% or more, preferably 15toa+Ic% or more.

When we examined the above findings in terms of the hydrogen atom content and the ratio of crystal grain area per unit volume in the film shown in Figure 5, we found that hydrogen atoms (H
) with a content in the range of 1 to 4 atomic%,
The proportion of grain area per unit volume was found to be in the range of 65-85% by volume.

From these results, it has been found that the electrical properties of a film composed of Zn5e:H are influenced by the content of hydrogen atoms (H) in the film and the ratio of crystal grain area per unit volume in the film. In order for the film to have electrical properties that can be suitably applied to devices such as solar cells, the hydrogen atom (H) content in the film must be 1 atomic%.
It has been found that it is necessary to satisfy both the requirements that the film be 4 atomic % and that the ratio of the crystal grain area per unit volume in the film be in the range of 65 vol % to 85 vol %.

(1) Raw material gas (A
) with LiC5H 1. O x 1 0-1. mol/
min. S formed on an St single crystal wafer in the same manner as in A above except that the conditions used in
Zn5e on i 02 Ill and on quartz glass substrate:
H: Forming Li1ll, Sample No. 13-24
and samples No. 13' to 24' were prepared, respectively.

(2) For each of sample No. 13' to 24' (deposited film samples on quartz glass substrate), cut the sample in half, and place a comb-shaped electrode of A1 on the film surface of one of the cut sample parts under vacuum. It was deposited by a vapor deposition method, and the dark conductivity of the film was measured. Regarding the remaining cut sample, the hydrogen atom content in the film was measured in the same manner as in A above.

The above measurement results are summarized in FIG.

In the figure, the white circle (0) indicates Zn5e:H:Li1l, which was measured after film formation without any history of irradiation with light stronger than indoor light.
The dark conductivity of AM-1 (
The values of the dark conductivity of the Zn5e:H:Li film measured at °C after continuous 8-hour irradiation with 100ml/c2) are shown.

Also, the aforementioned Aj! - For each sample on which a comb-shaped electrode was deposited, the conduction type was determined by thermoelectromotive force measurement, and the H content in the film was 0.25 ato+*lc%.
Larger samples showed p-type conductivity. ll
Samples in which the H content in 11I was less than 0.08 atomlc% showed weak n-type conductivity.

(3) For each of samples No. 13 to 24, the ratio of crystal grain area per unit volume in the film was observed using the same method as in case A above, and it was found that the hydrogen atom content in the film and the The relationship with the ratio of crystal grain area per unit volume was the same as that of the non-doped film, and the relationship curve shown in FIG. 9 was obtained.

(4) From the results shown in FIGS. 8 and 9, it can be seen that a film with good doping efficiency contains a region of amorphous grains of 15% by volume or more. That is, it can be seen that a film with good doping efficiency requires a region of amorphous grains of 15% by volume or more.

In other words, if there are few amorphous grains, the flexibility of the structure will be insufficient, and the structure at the interface between grains will not be sufficiently relaxed, resulting in an increase in defects such as dangling bonds. Put it away.

If a dopant is doped there, the dopant will aggregate at the grain interface, and will not enter the interior of the grain, and even if it is introduced into the film, the desired valence electron control and dark conductivity shift will not be achieved. It will no longer be done.

On the other hand, when dangling bonds are terminated with hydrogen atoms (H) and amorphous grains exist at a ratio of 15% by volume or more at grain boundaries or within grains,
Flexibility is provided in the structure, where the above-mentioned defects at grain boundaries are reduced. For this reason, as will be described later, the change in dark conductivity when a dopant is added, that is, the doping efficiency, is much better than that of a film without amorphous grain regions. Note that the area of amorphous grains is 1
In the case of a film having less than 5% by volume - the structure has insufficient flexibility, making it easy for the film to peel off from the substrate.

From these facts, it has been found that it is necessary for the amorphous grain region to exist in the film at a ratio of 15% by volume or more.

(5) In the same manner as in (1) above, sample No.
25-36, sample No. 37-48 and sample No. 49
~60 (on SIOzllI), and sample No. 25'
~36', sample No. 37'~48' and sample No.
, 49' to 60' (on a quartz plate) were prepared.

The dark conductivity of each of samples Nos. 25 to 60 was measured using the same method as described above without any history of irradiation with strong light, and the measurement results are summarized in FIG. 10. 1st
From the results shown in Figure 0, it was found that the value of dark conductivity varied greatly depending on the film forming conditions, and the variation was particularly significant in the region where the amount of H2 gas immersion was large.

On the other hand, with respect to samples No. 25' to 60'e (D), almost no variation was observed in the measurement results of the hydrogen atom content in the film and the observation results of the ratio of the crystal grain area.

For sample Nos. 25" to 60', the areas where the dark conductivity varied greatly were the H2 flow rate of 305 ec
- Under the above film forming conditions, the hydrogen atom content in the film exceeded 4atolc%, and the ratio of the crystal grain area was 65% by volume, which was an ungrooved film.

From the above results, the following points were understood.

In other words, when the ratio of the amorphous grain region per unit volume in the film exceeds 35% by volume, the electrical contact between the crystal grains is interrupted and conduction is determined mainly by the amorphous grain region.
Therefore, the dark conductivity becomes low.

Because of this, the range of applications as a device is ultimately narrowed.

In addition, the control of valence electrons and the change in dark conductivity due to the doped dopant are significantly different between the crystal grain region and the amorphous grain region, making it difficult to obtain the desired control of valence electrons and change in dark conductivity.

That is, when a doped dopant is introduced into an amorphous grain region rather than a crystal grain region, large variations in characteristics occur, which causes a problem in that the desired dark conductivity cannot be obtained.

Further, the reason why the dark conductivity changes greatly when intense light is irradiated as shown in FIG. 8 can be understood from the following. That is, when the amorphous grain region exceeds 35% by volume, the hydrogen atom content in the film is significantly large.
Therefore, due to changes over time, boundary changes, etc., hydrogen atoms in the film are likely to be desorbed, and when such desorption occurs, the result is a phenomenon in which the properties of the film deteriorate.

Considering the above, in order for the Zn5a:H film to have good reproducibility and desired stable film quality, the hydrogen atom (H) content in the film must be 46 to 1 c% or less, and It can be seen that the ratio of the crystal grain area per unit volume in the film needs to be 65% by volume or more.

(6) A Zn5e:H film and a Zn5e:H:Li film were formed on a quartz glass substrate by variously changing the film formation conditions using the same method as in (1) above. The relationship between the hydrogen atom content in the film and the ratio of crystal grain regions in the film, and the relationship between the hydrogen atom content in the film and the electrical properties (
We investigated the relationship between the rate of change in conductivity under AM-1 irradiation, hole drift mobility, dark conductivity, etc., and found that the hydrogen atom content in the film and the A strong correlation was found between the electrical properties and the hydrogen atom content in the film, and the optimal hydrogen atom content in the film was 1 to 4 atoms/1c%. I found out something. on the other hand,
The ratio of the crystal grain area in the film that satisfies the hydrogen atom content in the film specified here is preferably 65 to 85.
It has also been found that it is desirable that the amount is preferably 70 to 80% by volume.

(11) Next, the two types of substrates are simultaneously set in parallel at predetermined positions of the substrate holder 202 of the known device shown in Figure Is2, and Zn is deposited on the substrates under the film forming conditions shown in Table 3.
5a+-, Te, :H9i was formed to form samples N011-1.
2 and samples No. 1' to 12' were prepared.

(1) Extended l' and 11 (+1 board, thickness 0.5mm, I 1nc
hφ size circular low resistance (resistivity ρ-10″″Qc
The wafer was thermally oxidized in a 02 gas atmosphere at 1000°C to form about 5000 sto, Ill on a p-type St single crystal univer (approximately 5,000 m). A quartz glass substrate with a size of 2.5 cm square was prepared.

Table 3 (+l+1, then samples N091-1 on Si wafer
2 was cut in half, and each of the cut parts was cut into a size of 5 squares to fit the holder of rF-M (i31 transmission electron microscope).
The deposited film side was brought into contact with the surface of a glass plate having a size of m x 50 mm, and the deposited film side was fixed using wax so that the part on the deposited film side could be seen from the other side of the glass plate.

(iV) then 1(F%HNOs, CH3CO0H
A mixed solution of IF and water, in which the concentration of IF is adjusted with water, is prepared, and the sample prepared in the above (111) is treated with the exposed part of the Si-single crystal wafer using the mixed solution. was etched. At that time, the etching rate was controlled by changing the concentration of HF in the mixed solution.

The etching process was completed when a portion of the St-single crystal wafer was completely etched away by applying light from the deposited film side and observing the state of the transmitted light.

(V) After etching the sample, the wax was dissolved away using an organic solvent (toluene), the deposited film was removed from the glass plate, washed with water, air-dried, and S i Ox
A test sample consisting of a Zn5e, -x Ta, :H film on tll was obtained.

(2)! (1) above about what happened
Each of the test samples for samples Nos. 011 to 12 above was fixed to a sample holder of a TEM (acceleration voltage: 200 keV), a transmission image was formed, and the image was observed. The obtained transmission image contains Zn5a++ll Te
II: A lattice image with very little lattice disorder was observed where a crystal grain region existed in Hlli. moreover,
This lattice image is Z n S a 1-1 IT ew :
It was evenly distributed in all parts of Hlli.

Based on the lattice image, measure how many crystal grain regions are present per certain area of the test sample, and calculate the ratio of crystal grain regions for the deposited JI film as volume % (Vol, %).
It was calculated and evaluated.

At this time, for confirmation, the orientation of the crystal grains and the size of the crystal grain region were measured using X-ray diffraction, and these measurement results were also referred to.

(3) 1 is also standing. (1) In (1)-(i) above, the samples No. 1' to 12' prepared on the quartz substrate are cut in half, and each sample is placed in a vacuum chamber. Put it in the room, 1QQQ'c above room temperature.
The amount of hydrogen atoms (H) released from the sample was determined using a mass spectrometer. As a standard sample, a sample was used in which a predetermined amount of H ions were implanted into a sample prepared under conditions that did not contain H at all.

(-11'J Also, sample No. 1 for TEM observation,
The distribution state and elemental composition of Zn atoms and Se atoms in the deposited film were analyzed for each sample using an X-ray microanalyzer (manufactured by Shimadzu Corporation, hereinafter abbreviated as "XMA"). The measurement results were as shown in Table 4. In addition, in the measurement, % Z n s S
e % Te Because it was determined as a matrix of only e, H etc. in the film were excluded from the calculation.

Judging from the above measurement results, Zn atoms, Se atoms, and T
e atoms are uniformly distributed, Zn atoms and (Se atoms +
It was found that the composition ratio of Zn (Te atoms): (Se+Te) was approximately 1:1 and satisfied the stoichiometric relationship.

Also, the composition ratio of Se atoms and Te atoms: Ss:Te=2
:8.

The measurement results for (2) and (3) above in Table 4 (4) are summarized in Figure 11. From the results shown in FIG. 11, it can be seen that ZnS e
l-w Tea: As the content (atomic%) of hydrogen atoms (H) in Hllll (X=0.8) increases, the ratio of crystal grain area per unit volume in the film decreases, and the The hydrogen atom content of is 0, 1 stomI
It was found that in the range of c% to 10 atoa+lc%, the proportion of grain regions in the film per unit volume ranged from 90% by volume to 40% by volume.

In addition, in the preparation of the sample in (1) above, if the H2 gas flow rate is set to 0.05 scc or less, the deposited film that is formed will be a film composed mostly of Zn, and
When the flow rate of the two gases was 251 m or more, no deposited film was formed.

For each of the remaining half samples No. 1' to 12' formed on the quartz substrate in (1) to (1i) above, interdigitated electrodes of AIL were evaporated, and the dark conductivity of the film was measured. The results are summarized in FIG. 12. From the results in Figure 12, looking at the change in electrical conductivity a after 8 hours under AMl, 5 irradiation light, we find that the ratio of the value a after 8 hours to the initial value a0 is Δσ = a / a. The rate of change in dark conductivity when looking at the content of hydrogen atoms (H) in the film is 8
It was found that the amount increased more rapidly than at atoa+ic%, and it was also found that at 4 atomic% or less, there was almost no change in the characteristics due to light irradiation.

Next, in (1)-(ii) above, 5i0211! formed on the Si-wafer! Zn deposited on top
S eo2T ea,a: For each of the remaining half of Hf1i samples N001 to 12, a semitransparent film of AIL was deposited, and a pulse voltage was applied between the An-Si-wafer so that Ajl became negative. , 1nse
When the drift mobility of holes was measured by the time-of-flight method by irradiating a light pulse of UV light of approximately 300 nm, the dependence results as shown in FIG. 13 were obtained.

From the results shown in Figure 13, it can be seen that the hydrogen atom content in the film is 0,
It was found that the hole drift mobility is an extremely small value below 5 atomic%, and a large value is obtained when the hydrogen atom content in the film is in the range of 1 atomic% to 8 atoIlic%. Furthermore, it was found that when the hydrogen atom content in the film was 8 ato+aic% or more, the value of drift mobility decreased, albeit gradually.

From the above results, the hydrogen atom content in the film is 8 atomic% or less, preferably 4 atomic% or less, from the viewpoint of property changes due to light irradiation, and from the viewpoint of hole mobility, it is 0.5 atomic% or less. atomic% or more, preferably 1 atomic% or more.

When we examined the facts found above in terms of the hydrogen atom content in the film and the ratio of crystal grain area per unit volume in Figure 11, we found that Z n S e + -w T e X : H
The content of hydrogen atoms (H) in the film composed of is 1 to 4.
In the atomic% range, the proportion of grain area per unit volume was found to be in the range of 65 to 85% by volume.

Therefore, the electrical properties of a film composed of Zn5e+-, Te, and :H are influenced by the content of hydrogen atoms (H) in the film and the ratio of crystal grain area per unit volume in the film. It was found that in order for the film to have electrical properties that can be suitably applied to devices such as solar cells, the content of hydrogen atoms (H) in the film must be 1 s.
atomic% to 4 atomic%, and the ratio of crystal grain area per unit volume in the film is 65% to 85% by volume.
It has been found that it is necessary to satisfy both requirements of being within the range of % by volume.

(1) Raw material gas (A
) with 1.0 x 10-” mol/m of LiC5Hy
StO formed on the St-single crystal unibar in the same manner as in A above except that the conditions used in ln were added.
, Zn5e on the film and on the quartz glass substrate, -x Tl!
III:H:Li1li was formed and sample No.
, 13-24 and samples No. 13'-24' were prepared, respectively.

(2) For each of sample No. 13' to 24' (deposited film samples on quartz glass substrate), cut the sample in half, and attach an Af2 comb-shaped electrode to the film surface of one of the cut sample parts under vacuum. It was deposited by a vapor deposition method, and the dark conductivity of the film was measured. Regarding the remaining cut sample, the hydrogen atom content in the film was measured in the same manner as in A above.

The above measurement results are summarized in FIG. 14.

In the figure, the solid line indicates Zn5e+-xTe, :H:L, which was measured after film formation without any history of irradiation with light stronger than indoor light.
The value of the dark conductivity of i1li is shown, and the dashed line is AM −1,
5 (10C1@W/cm") measured after continuous irradiation for 8 hours. Zn5a+-++ Tea: H: Li1l
The dark conductivity value of i is shown.

Furthermore, for each of the samples on which the Af comb-shaped electrodes were deposited, the type of conduction was determined by thermoelectromotive force measurement. In the samples where the H content in the film was greater than 0.25 atomic%, p-type conduction was observed. The model was shown. Samples in which the H content in IIi was 0.08 atomic% or less showed weak n-type conductivity.

(3) For each of samples No. 13 to 24, the ratio of crystal grain area per unit volume in the film was observed using the same method as in case A above, and it was found that the hydrogen atom content in the film and the The relationship between the ratio of grain area per unit volume of
The relationship curve shown in the figure was obtained.

(4) From the results shown in FIGS. 14 and 15, it can be seen that a film with good doping efficiency contains a region of amorphous grains of 15% by volume or more. That is, it can be seen that a film with good doping efficiency requires a region of amorphous grains of 15% by volume or more.

In other words, if there are few amorphous grains, the flexibility of the structure will be insufficient, and the structure at the interface between grains will not be sufficiently relaxed, resulting in an increase in defects such as dangling bonds. Put it away.

If a dopant is doped there, the dopant will aggregate at the grain interface, and will not enter the interior of the grain, and even if it is introduced into the film, the desired valence electron control and dark conductivity shift will not be achieved. It will no longer be done.

On the other hand, when 15% by volume or more of amorphous grains in which dangling bonds are terminated with hydrogen atoms (H) exist at the interface, flexibility is imparted to the structure and the above-mentioned problems at grain boundaries occur. This results in fewer defects. For this reason, as will be described later, the change in dark conductivity when a dopant is added, that is, the doping efficiency, is much better than that of a film without amorphous grain regions. In addition, in the case of a film in which the amorphous grain region is 15% by volume ungrooved,
Since the structure has insufficient flexibility, the film tends to peel off from the substrate.

Based on these facts, it has been found that it is necessary to have an amorphous grain region of 15% by volume or more in the film.

(5) In the same manner as in (1) above, sample No. 2
5-36, Sample No. 37-4B and Sample No. 49-
80 (on sto2 membrane), and sample No. 25' to 36
', Sample No. 37' to 48' and Sample No. 49'
~60' (on a quartz plate) were each produced.

The dark conductivity of each of samples Nos. 25 to 60 was measured using the same method as described above without any history of irradiation with strong light, and the measurement results are summarized in FIG. 16. 1st
From the results shown in FIG. 6, it was found that the dark conductivity value varied greatly depending on the film forming conditions, and the variation was particularly large in the range where the H2 gas flow rate was small.

On the other hand, in the measurement results of the hydrogen atom content in the films and the observation results of the ratio of crystal grain areas for Samples Nos. 25' to 60', almost no variation was observed.

For sample No. 25' to 60'', the areas where the dark conductivity varied greatly were the H2 flow rate of 3 o 5.
Under the film forming conditions where the flow rate was higher than cca+, the hydrogen atom content in the film was 5 atomic % or more, and the ratio of the crystal grain area was 65 vol %, which was an ungrooved film.

From the above results, the following points were understood.

In other words, when the ratio of the amorphous grain region per unit volume in the film exceeds 35% by volume, the electrical contact between the crystal grains is interrupted and conduction is determined mainly by the amorphous grain region.
Therefore, the dark conductivity becomes low.

Because of this, the range of applications as a device is ultimately narrowed.

In addition, the valence electron control and dark conductivity changes due to the doped dopant are significantly different between the crystal grain region and the amorphous grain region, making it difficult to obtain the desired valence electron control and dark conductivity change. .

That is, when a doped dopant is introduced into an amorphous grain region rather than a crystal grain region, large variations in characteristics occur, which causes a problem in that the desired dark conductivity cannot be obtained.

Also, when strong light is irradiated as shown in Figure 14,
The reason why the dark conductivity changes greatly can be understood from the following points. That is, the area of amorphous grains is 35% by volume.
If it exceeds the hydrogen atom content in the film, the hydrogen atom content in the film is extremely large, and as a result, desorption of hydrogen atoms in the film is likely to occur due to changes over time, boundary changes, etc., and when such desorption occurs, The result appears as a phenomenon of deterioration of film characteristics.

Considering the above, Z n S fs l −It
In order for T e *:H@ to have good reproducibility and desired stable film quality, hydrogen atoms (
) I) content is required to be 4 atomic % or less, and the ratio of crystal grain area per unit volume in the film is required to be 65 vol % or more.

(6) ZnSa was deposited on a quartz glass substrate using the same method as in (1) above while varying the film formation conditions.

Tel1:Hlli and Zn5e+-xTe,:
H:Li films were respectively formed, and the relationship between the hydrogen atom content in the film and the ratio of the crystal grain region in the film, and the hydrogen atom content in the film and the electrical properties (AM- 1) We investigated the relationship between the rate of change in conductivity under irradiation, hole drift mobility, dark conductivity, etc., and found that
The hydrogen atom content in the film and the ratio of crystal grain regions in the film that were specified from the above experiments were almost satisfied, and a strong correlation was found between the electrical properties and the hydrogen atom content in the film. The hydrogen atom content in the film is 1 to 4 ato
It was found that mic% was optimal. On the other hand, the proportion of crystal grain regions in the film that satisfies the hydrogen atom content specified herein is preferably 65 to 85% by volume, more preferably 50 to 80% by volume. It was also found that this is desirable.

(1) Preparation of sample (i) A 2.5 cm square quartz glass substrate was prepared as a substrate.

(i l) Next, the substrate was set in a predetermined position on the substrate holder 202 of the known device shown in FIG. 2, and Zn5el-, TeU: H
A sample was prepared by forming M (0≦X≦1). The sample name is L-N.
It represents the flow rate ratio of ESe, DE, and Te, and the H2 gas flow rate is L-1 to 12 of 12fI, DES, e, and DE.
The flow rate ratio of Te is 11 types from N-1 to 11, and the combination is 132f! It was classified as a kind.

(2) Measurement of H content and composition ratio of Zn, Ss, and Te in the film (1) Samples 1-1 to 12-11 prepared on the quartz substrate in (11m ('I)) were cut in half. Each sample was placed in a vacuum chamber, heated from room temperature to 1000°C, and the amount of hydrogen (H) released from the sample was determined using a mass spectrometer.As a standard sample, a sample prepared under conditions that did not contain any H was used. A sample into which a predetermined amount of ions had been implanted was used.

Table (it) Also, using the remaining half of the sample, an X-ray microanalyzer (manufactured by Shimadzu Corporation, hereinafter referred to as "XMA
) in the deposited film for each sample.
The distribution state and elemental composition of n atoms, Se atoms, and Te atoms were analyzed.

Judging from the measurement results, Zn atoms, Se atoms, and T
e atoms are uniformly distributed, Zn atoms and (Se atoms +
It was found that the composition ratio Zn:se+Te (Te atoms) was approximately 1:1, satisfying the stoichiometric relationship.

Also, in all samples -DeSes+1.5x10
-'x (1-X)mol/mln, DETe-1,O
By setting the flow rate to x10-'x Xmol/win, a deposited film in which the atomic ratio of Ss and Te in the film was approximately (t-X):X could be produced.

(3) Measurement of photoconductivity (2) AfL interdigitated electrodes with a gap of 0.2 sII were deposited on the sample on the quartz substrate used in the measurement of (11), voltage tOV was applied, and AM-1,5 light was irradiated. The current was measured under , and the photoconductivity δp of Zn5e, -, :Tew :H was determined. Figure 17 shows the dependence of δp on the hydrogen atom content with X as a parameter, and Figure 18 shows the dependence of δp on the hydrogen atom content with X as a parameter.
The X dependence of δp of the film near atomic% is shown.

From the above experimental results, the hydrogen atom content in the film is 1 to 10
atomic% and X is 0.7≦X≦0.9, that is, the ratio of Ss to Te is in the range of 3=7 to 1:9, and δp is particularly thick, making it suitable as an i-type semiconductor layer of a pin-type photovoltaic element. It was found that the following characteristics can be obtained.

(1) Preparation of sample In Table 5, LiC3H is used as the raw material gas (A).

A sample was prepared in the same manner as in section D-(1) except that 1 and Ox 10-"+aol/ain were added.

(2) Measurement of the H content in the film and the composition ratio of Zn, Se, and Te. Using the same method as in section D-(2), the H content, the distribution state of Zn atoms, Se atoms, and Te atoms, and the distribution state of Zn atoms, Se atoms, and Te atoms in the deposited film were measured. Elemental composition analysis was performed.

Judging from the measurement results, Zn atoms, Se atoms, and T
e atoms are uniformly distributed, Zn atoms and (Se atoms +
The composition ratio Zn:Se+Te (Te atoms) is approximately 1:1, which satisfies the stoichiometric relationship.

Also, DeSe=1.5x10-' in all samples
x (1-X) mol/mln, DETa=1. O
A deposited film in which the atomic ratio of Se to Te in the film was approximately (1-X):X could be produced by setting the flow rate to x10-'x Xmol/m1n.

(3) Measurement of dark conductivity A comb-shaped electrode of A1 with a gap of 0.2□ was deposited on the sample on the quartz substrate used in the measurement of (i +) in (2), a voltage tOV was applied, and a current was measured in the dark. measured, Zn5e+-,
The photoconductivity δp of :Te and :H was determined. FIG. 19 shows the dependence of δp on the hydrogen atom content with X as a parameter.

Further, when the conduction type was determined by thermoelectromotive force measurement, the conductivity type was found to be p-type in samples in which the hydrogen content in the film was greater than 0.25 atomic%.

Further, FIG. 20 shows the X dependence of δp in a film with a hydrogen content of around 2 atomtc%.

From the above experimental results, the hydrogen atom content in the film is 1 to 10
When atoIIlic% and X is 0≦X≦0.
1. It has been found that excellent p-type conductivity can be obtained when the ratio of Se to Te is in the range of 1:0 to 9:1 and 3:7 to 1:9. Ta.

(1) Preparation of sample In Table 5, (C2H8)3Aj2 is added to the raw material gas (A).
(TEAIl) 5 x 10-”a+ol/a+i
A sample was prepared in the same manner as in section D-(1) except that n was added.

(2) Measurement of the H content in Ili and the composition ratio of Zn, Se, and Te Using the same method as in section D-(2), we measured the H content in the deposited film, the distribution state of Zn atoms, Se atoms, and Te atoms, and Elemental composition analysis was performed.

Judging from the measurement results, Zn atoms, Se atoms, and T
e atoms are uniformly distributed, Zn atoms and (Se atoms +
It was found that the composition ratio of (Te atoms) was approximately 1:1, satisfying a stoichiometric relationship.

Also, in all samples DeSe=1.5X10-'
x (1-X) mol/min, DETezl, O
By setting the flow rate to x10-'x Xmol/win, a deposited film in which the atomic ratio of Ss and Te in the film was approximately (t-x):X could be produced.

(3) Measurement of dark conductivity An interdigitated An electrode with a gap of 0.2□ was deposited on the sample on the quartz substrate used in the measurement of (it) in (2), and a voltage of 1
Applying 0V and measuring the current in the dark, Zn5et-X
The photoconductivity δp of :Tex :H was determined. Furthermore, when the conduction type was determined by thermoelectromotive force measurement, all samples showed n-type conduction type.

When we investigated the dependence of δρ on the hydrogen content, we found that p-type Z
n5e+-1lTe,: As with the H film, the maximum δp for each X is within the range of 1 to 10 atomic% hydrogen content.
was gotten.

δ for X in a film with hydrogen content of 2 atomic%
The dependence of p is shown in Figure 21. From Figure 21, all S
It can be seen that excellent δp is obtained in the range of the amount ratio of e and Te.

(Preparation of +1 sample In Table 5, the hydrogen flow rate was fixed at the condition of 15 sec + a, and a series of Z n S e 1-w T ex was carried out on the quartz substrate by changing X without flowing the doping gas.)
(The membrane was created.

(ii) Composition analysis of sample D- (Using the same method as in Section 21, measurement of the H content in the deposited film, measurement of the distribution state of Zn atoms, Se atoms, and Te atoms, and elemental composition analysis were performed.

The measurement results show that in all samples, Zn atoms, Se atoms, and Te atoms are uniformly distributed in the deposited film, and the composition ratio of Zn atoms and (Se atoms + Te atoms) is approximately 1:1. This means that the stoichiometric relationship is satisfied.

Also, DeSe=j, 5X10-' in all samples
x (1-X) mol/mln, DETe-1, Ox1
By setting the flow rate to 0-'x Xmol/ff1in, a deposited film in which the atomic ratio of Se to Ta in the film was approximately (t-X):X could be produced.

(I) Measurement of optical band gap The obtained samples were used to determine the change in absorption coefficient with respect to the wavelength indicated by *, and the optical band gap of each sample was determined from the absorption edge.

Z n S e I-x T for Se:Te amount ratio
ex :Hlli (H content: 2 atomic
%) is shown in FIG. 22.

It can be seen that a film in which the amount of Se:Te is 7:3 or more has an optical band gap in the range of 2.3 to 2.2 ev.

k, non-doped and n-type doped (1) Preparation of sample St wafer whose surface was oxidized by thermal oxidation method. A Zn5e+-x TAX:H film was fabricated on a quartz substrate. However, p-type Z n S e r
-m T e II: Li when creating Hill
C5Hy as n-type Z n S a t-8Tam:Hl
When making li, use TEAll [(C2H4)s AIt
1 was added to the raw material gas (A), respectively. Furthermore, these gases were not added when producing non-doped Zn5el-11Te, :Hllll.

(2) Measurement of H content in Iti and composition ratio of Zn%Se%Te Using the same method as in section D-(2), the distribution state of H content Zn atoms, Se atoms, and Te atoms in the deposited film and Elemental composition analysis was performed. The H content was approximately 2 in all sample amounts.
Ato111c%. In addition, the measurement results show that Zn atoms, Se atoms, and Te atoms are uniformly distributed in the deposited films for all samples 1-1 to 12-11, and the composition of Zn atoms and (Se atoms + Te atoms) is It was found that the ratio was approximately 1:1, satisfying a stoichiometric relationship.

In addition, DeSexl, 5x1 (M
'x (1-X) mol/m1n, DETaxl,
By setting the flow rate to Ox10-'X

(3) Evaluation of the ratio of the crystal grain area of each sample The lattice image was observed by TEM according to the procedure described in section A-(1), and the ratio of the crystal grain area was evaluated. Z n calculated from the results
S e l-M T ex : The dependence of the proportion of the crystal grain region in oM on X (proportion of Te) is expressed as
Illustrated.

The present invention, which was completed based on the above experimental results, firstly, as mentioned above, uses zinc atoms (Zn) and selenium atoms (S
e) and at least a hydrogen atom (H),
Containing the hydrogen atoms in an amount of 1 to 4 atomic%,
The ratio of crystal grains per unit volume is 65 to 85 volume (vol
, )%, a pin junction photovoltaic device using at least an excellent functional deposited film composed of a substance expressed as Zn5e:H as an l-type semiconductor film, and secondly a zinc atom (Zn) and selenium Atom (Se) and tellurium atom (
Te) and at least hydrogen atoms (H), the amount ratio of Ss and Te is in the range of 37 to 1:9 in terms of atomic ratio, and the hydrogen atoms are contained in an amount of 1 to 4 atomic%, The ratio of crystal grains per unit volume is 65 to 85 volume (
The present invention relates to a pin junction photovoltaic device using an excellent functional deposited film made of a substance expressed as Zn5e:H, which has a vol.

The above-mentioned functional deposited films of the present invention are highly versatile, and can be deposited on an appropriate plate-shaped or cylindrical support depending on the application, or can be deposited on such a support. It can also be deposited on a semiconductor film formed on the body.

Zn5a:Hlll according to the present invention contains Zn atoms, Se atoms, and Te atoms in a uniform distribution state in the film with the composition ratio of both atoms satisfying the stoichiometric ratio, and 1 to 4 atoms.
ic% of hydrogen atoms, possibly in a free state, by suitably terminating dangling bonds of Zn atoms and/or Se atoms, and containing hydrogen atoms in crystal grain regions and amorphous grain regions. and the crystal grain region is uniformly distributed in the film and the ratio of the crystal grains per unit volume of the film is 6.
It has a diameter of 5 to 85% by volume and is highly uniform in structure and composition.

Moreover, the Zn5e+-xTe, :H film according to the present invention has Zn5e+-xTe, :H film.
n atom and S, e atom and Ta atom, Znl1i (child and (
The composition ratio of (Ss atoms + Ta atoms) satisfies the stoichiometric ratio and is contained in a uniform distribution state in the film, and the quantitative ratio of Se and To is in the range of 3 nia to 1:9 in terms of atomic ratio. In addition, dangling bonds of Zn atoms and/or Se atoms and Te atoms are suitably terminated with hydrogen atoms in an amount of 1 to 4 atomIc% (however, in some cases, hydrogen atoms in a free state may be eaten). ), and has a crystal grain region and an amorphous grain region, the crystal grain region is uniformly distributed in the film, and the ratio of the crystal grains per unit volume of the film is 65 to 85% by volume. It is highly uniform in structure and composition.

The Zn5e:H film and Zn according to the present invention thus obtained
5sl-1lTax: The H film is one in which the stress generated in the entire film is alleviated to a desired state, has extremely excellent electrical and mechanical properties, and has excellent adhesion to the support and good resistance to other films. It has excellent adhesion.

Furthermore, the conventional Zn5e film and ZnSeIt
In the TeIl film, it is difficult to introduce dopants, so the Zn5a film and Zn5l! + +lj It was difficult to make Ten Ill a desired conductivity type, but as mentioned above, in the present invention, dangling bonds are reduced to a desirable state, making it possible to introduce dopants and The aforementioned Zn5e-based and Zn5e+-tTeIl, system films, ie, Zn5e:H1l!, allow easy and efficient introduction of dopants. ! and Zn5e+−, Te1I
:Hllll, it has excellent p-type and n-type semiconductor properties, and as mentioned above, the stress is relaxed to the desired state, and it has extremely excellent electrical and mechanical properties. p-type and n-type Zn5a:H:M, which also has excellent adhesion to the support and other films.
p and Zn5q, −, Te, +: H: Mp (
However, Mp means a dopant. ) Zn5e:H:Mp film of the present invention and Z
n5e,-,Te,: H: MPI! In particular, Mp or p-type dopant is an element of group I-A, i.e.
Li, Na, K and Rb, elements of group I-B, i.e. Cu
and Ag or elements of group V-A, namely P, As and sb
It can be any material selected from among these, among which Li, P, and As are preferred. And Mp in the membrane
From the viewpoint of a p-type semiconductor for pin junction, the amount of is preferably 50 to 1 x 10', atomlc
ppm, more preferably 5 x 10'' to 10.'
ato+sic ppm, optimally 103~5X
10' atomic pp-.

Also Zn5e:H:Mn and ZnS e , -1
lTe, :H:Mn (However, Mn means an n-type dopant.) For the film, Mn in that case is an element of group 1II-B of the periodic table, namely B, AJ2, Ga
and In, elements of the 1st V-B group, i.e. SL, Ge%
C and Sn, elements of group ■-B, i.e. F, C11, B
It can be any selected from r and ■, but A1, Ga, In and B are particularly preferred.

The amount of Mn in the film in the above case is preferably 50 to 1 from the viewpoint of an n-type semiconductor for pin junction.
x 10' atomic ppm, more preferably 5 x 102 to IQ' atomic ppm, optimally 103 to 5 x 10'' atomic ppm
It is +.

As mentioned above, the functional deposited film in the present invention is characterized by the content of hydrogen atoms in the film and the ratio of crystal grain area per unit volume both falling within specific ranges. However, regarding the content of hydrogen atoms,
If it is less than 1 stomlc%, the amount of dangling bonds will increase and become undesirable.
If it exceeds atomic%, lattice disorder and voids will occur, increasing the number of defects, and in either case, a deposited film with desired properties cannot be obtained.
Also, regarding the ratio of crystal grain area, it is 65% by volume.
If the amount is smaller, the absolute amount of crystal grains, which is one of the factors that affect the improvement of electrical properties, decreases, and it increases to 85
If the volume exceeds %, the crystal grains will directly join together, forming so-called grain boundaries.
In either case, a deposited film having desired properties cannot be obtained.

Zn5e according to the present invention: Hill, Zn5e:
H: M film, Zn5e, -, Te1l: H film and Z
n S e l −X T e *: H: M film (However, M risks p-type or n-type dopants.)
Regarding its composition and structure, defects in the film can be extremely reduced by making the deposited film contain a specific amount of hydrogen atoms and controlling the ratio of crystal grains per unit volume to a predetermined value. Its electrical conductivity is that of conventional Z
n5elli, Zn5e: M film, Zn5e+-w T
This is significantly improved compared to the e11 film and Zn5e+-x Te:Mlll.

This can be clearly seen for Zn5el-, Te++ :H:Mp@. In other words, in p-type doping, x (ratio of Te) is O as shown in Figure 20.
When the composition ratio is in the range of ≦X≦1.0.7≦X≦1.0, a large δd is obtained and an improvement in doping efficiency is observed,
As shown in Figure 23, when X is within this range, the ratio of crystal grains is 65vo1% or more, and doping efficiency can be optimized by controlling the ratio of crystal grains depending on the content of hydrogen atoms. I understand what happened. As for the non-doped Zn5e, -1lTell:H film, as shown in Figure 23, the proportion of crystal grains is high over the entire range of
The photoconductivity (δp) is extremely high in the range of 0.7<x<0.9 (ratio of Te), and the l
It is suitable as a type semiconductor layer. This is considered to be due to the fact that not only the ratio of crystal grains but also the localized level distribution in the forbidden band δp changes depending on X.

Therefore, the forbidden band width (band gap) of the Znse:H film is approximately 2.67 eV, and the forbidden band width (band gap) of the Zn5et-, Ten: Ill is approximately 2.3 to 2°4 eV. , all of them have values that are effective for absorbing short wavelength light, and by creating a layer structure that fully takes advantage of the above effects, it has high charge conversion efficiency for short wavelength light. A photovoltaic device can be formed.

The photovoltaic element of the present invention has a layered structure having a pin junction. If the pin junction is formed well between materials with a large band gap, a high Voc (open circuit voltage) can be obtained as a photovoltaic device. Improved Zn5e: Hllt or ZnSet-*
Tem: HIIl is used as at least an i-type semiconductor layer, and the Zn5e is also used as a p-type and n-type semiconductor layer.
:H film or ZnSe, -.

Tex: A semiconductor deposited film having a band gap as large as that of Hill's semiconductor layer and good electrical characteristics is used.

As mentioned above, Zn5e:H:M layer and ZnS
e r -t T e *: H: MN is suitable as a p-type and/or n-type semiconductor layer because of its excellent electrical properties. In particular, as a p-type semiconductor layer, one with good characteristics and a wide band gap has not been well known, and its usefulness is remarkable.

However, it is of course possible to use semiconductor films other than these as the p-type and/or n-type semiconductor layers.

That is, as the semiconductor deposited film having n-type conductivity, ZnO1ZnS and Zn5e are used, and as the semiconductor deposited film having p-type conductivity, ZnO1ZnS and Zn5e are used.
Each deposited film of nTe and CdTe is used. Of course, these deposited films can be made n-type or p-type by adding a dopant to each corresponding material film as necessary. For example, n-type dopants include Cu2, Br, Al, etc.
2 is used, and if Zn5a, Br, Ga, All
is used. For ZnTe, Cu and Ag%P are used as p-type dopants, and for CdTe, Li,
Sb and P are used.

The photovoltaic device of the present invention comprises the above-mentioned Zn5e:H film or Z
n5e+-, Tal1: By bonding the H film with the semiconductor deposited film described above, a high Voc can be obtained and high charge conversion efficiency for short wavelength light can be obtained.

Furthermore, since there are extremely few defects in the film, the transmittance for long wavelength light is increased, making it possible to obtain selective absorption of short wavelength light and high photoelectric conversion efficiency. This means that when the photovoltaic element of the present invention is applied to a solar cell, it emits relatively short wavelength light, such as a white fluorescent lamp, compared to a solar cell constructed from conventional A-3i. High photoelectric conversion efficiency can be achieved even when used under a light source that has many spectral components.
Even when used under sunlight, by using the photovoltaic element of the present invention as a cell on the light incident side of a tandem type or triple type solar cell, the photoelectric conversion efficiency of short wavelength light is significantly higher than before. It is possible to create a structure that can efficiently supply long-wavelength light to cells provided below. As a result, it is possible to create a layered structure that can charge and convert almost all components of the sunlight spectrum. Furthermore, since both the structure and composition of the film are stable, the problem of photodegradation can be greatly improved.

Below, the above-mentioned Zn5e of the present invention: Hlli or Zn5e
+-, Te1I: Shows a curved example of the layer structure of a photovoltaic element using Hg as a p-type semiconductor film, an n-type semiconductor film, and an n-type semiconductor film, and the above p-type Zn5e:H:MP.
Membrane or p-type ZnSal-mTe, :H:MpH
! When using a p-type semiconductor film other than the above-mentioned n-type Zn
5e:H:Mn1lll or n-type Zn5e, -1lTe
The same applies when an n-type semiconductor film other than the x:H:Mn film is used.

The photovoltaic device of the present invention is not limited to these examples in any way.

FIGS. 1(A) and 1(B) are diagrams schematically showing typical examples of the layer structure when the functional deposited film according to the present invention is used as the photovoltaic element of the present invention.

In the example shown in FIG. 1(A), an electrode 102 is placed on a support 101.
, an n-type semiconductor layer 103, an i-type semiconductor layer 104, a p-type soil conductor layer 105, a transparent electrode 106, and a current collecting electrode 107 are provided in this order. Note that in the photovoltaic element, light is incident from the transparent electrode 106 side.

In the example shown in FIG. 1(B), a transparent electrode 106, a p-type semiconductor +1105, and an l-type semiconductor Fl1 are placed on a transparent support 101.
04, a photovoltaic element 100 in which an n-type semiconductor layer 103 and an electrode 102 are provided in this order. In the photovoltaic element, light is incident from the support 101 side.

Note that the n-type semiconductor layer and the p-type semiconductor layer can be used interchangeably depending on the purpose.

FIG. 1(C) shows a conventional A-Silli as a comparative example.
FIG. 2 is a diagram schematically showing a typical example of the layer structure of a pin-type photovoltaic element using a PIN type photovoltaic element.

In the example shown in FIG. 1(C), an electrode 102 is placed on a support 101, and an n-type A-3i semiconductor N108 is used.
, a photovoltaic element 111 in which an l-type A-3i semiconductor layer 109, a p-type A-3i semiconductor layer 110, a transparent electrode 106, and a current collecting electrode 107 are provided in this order. In the photovoltaic element, light is incident from the transparent electrode 106 side.

The configurations of these photovoltaic elements will be explained below.

The support 101 used in the present invention may be monocrystalline or non-single crystal, and may be electrically conductive or electrically insulating. Furthermore, they may be translucent or non-transparent; examples thereof include Fa.

Ni% Cr, An, Mo, Au% Nb% Ta.

Metals such as (2), Ti, Pt% pb, etc., or alloys thereof, such as brass, stainless steel, etc., can be mentioned.

In addition to these, examples include films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, and polyimide, glass, and ceramics.

Moreover, as a single crystal support, Sl, Ge is used.

C% NaCA, C1, LiF, Garb.

E nAs% I nSb% GaP% MgO1Ca
Examples include those obtained by slicing and processing a single crystal such as F1, BaFm, p-AlI303, etc. into a wafer shape, and those obtained by epitaxially growing the same material or a substance with a similar lattice constant on these materials.

The shape of the support body can be a plate shape with a smooth surface or an uneven surface, a long belt shape, a cylindrical shape, etc. depending on the purpose and use.
The thickness is appropriately determined so as to form a desired photovoltaic element and to have a vine shape, but if flexibility is required as a photovoltaic element, the thickness is within a range that can sufficiently exhibit its function as a support. can be made as thin as possible. however,
In terms of manufacturing and handling of the support, mechanical strength, etc.
Usually, the thickness is 10 μm or more.

In the photovoltaic device of the present invention, appropriate electrodes are selected and used depending on the configuration of the device. Examples of these electrodes include a lower electrode, an upper electrode (transparent electrode) 1, and a current collecting electrode. (However, the upper electrode here refers to the one provided on the light incident side, and the lower electrode refers to the one provided opposite the upper electrode with the semiconductor layer in between.) About these electrodes This will be explained below.

1 to 11 As for the lower electrode 102 used in the present invention, the surface on which light for photovoltaic generation is irradiated differs depending on whether the material of the support 101 described above is translucent or not. For example, if the support 101 is made of a non-transparent material such as metal, light for generating photovoltaic force is irradiated from the transparent electrode 106 side.), and the location where it is installed differs.

In the case of a layered structure as shown in FIG. 1(A), the support 101 and n
type semiconductor layer 103. However, if the support 101 is conductive, the support can also serve as the lower electrode.

However, even if the support 101 is conductive, if the sheet resistance value is high, the electrode may be used as a low-resistance electrode for current extraction or for the purpose of increasing the reflectance on the support surface for effective use of incident light. 102 may be installed.

In the case of FIG. 1(B), the support 101 is made of a light-transmitting material, and light is incident from the support 101 side. Therefore, for the purpose of current extraction, the lower electrode 102 is
It is provided on the uppermost layer when viewed from the support body 101.

In addition, when an electrically insulating material is used as the support 101, the support 101 and n
A lower electrode 102 is provided between the semiconductor layer 103 and the lower electrode 102 .

As electrode materials, 'Ag%Au, Pt%Ni.

Examples include metals such as Cr, Cu, AJ2, TI, Zn, Mo%W, etc., and thin films of these can be formed by vacuum evaporation, electron beam evaporation,
Formed by sputtering or the like. Further, 1. Care must be taken so that the formed metal thin film does not become a resistance component with respect to the photovoltaic element, and it is desirable that the sheet resistance value is preferably 50Ω or less, more preferably 10Ω or less.

Although not shown in the figure, a diffusion prevention layer such as conductive zinc oxide may be provided between the lower electrode 102 and the n-type semiconductor layer 103.As for the effect of the diffusion prevention layer, the electrode 102
The lower electrode 102 and the transparent electrode 1 provided across the semiconductor layer are not only prevented from diffusing into the n-type semiconductor layer, but also have a slight resistance value.
06 due to defects such as pinholes, and multiple interference caused by the thin film to confine incident light within the photovoltaic element.

(If part pole' seed) The transparent electrode 106 used in the present invention desirably has a light transmittance of 85% or more in order to efficiently absorb light sources such as sunlight and white fluorescent lamps into the semiconductor layer. It is desirable that the sheet resistance value is 100Ω or less so that the internal resistance of the photovoltaic element does not increase and impair its performance.
Materials with such characteristics include 5nOz, I n
tOs, ZnO1CdO.

Cdl Sn0m, ITO(Inz 03 +sno
, ) and other metal oxides such as Au%Aj! , a thin film made of a metal such as Cu in an extremely thin and translucent manner.

In FIG. 1(A), the transparent electrode is a p-type soil conductor layer 105.
In FIG. 1(B), a substrate 10 is laminated on top of the layer.
1, it is necessary to select materials that have good adhesion to each other. As a method for producing these, a resistance heating evaporation method, an electron beam heating evaporation method, a sputtering method, a spray method, etc. can be used, and the method is appropriately selected depending on the need.

Dandan L1111 The current collecting electrode 107 used in the present invention is as follows.

It is provided on the transparent electrode 106 for the purpose of reducing the surface resistance value of the transparent electrode 106. The electrode material is Ag, Cr.
%Ni, All, Ag%Au, TI.

Examples include thin films of metals such as Pt%Cu and Mo%W, or alloys thereof. These thin films can be used in a stacked manner. Further, the shape and area of the semiconductor layer are designed so that a sufficient amount of light incident on the semiconductor layer is ensured.

For example, it is desirable that the shape spreads uniformly over the light-receiving surface of the photovoltaic element, and that its area is preferably 15% or less, more preferably 10% or less of the light-receiving area.

Further, the sheet resistance value is preferably 50Ω or less, more preferably 10Ω or less.

Hereinafter, the P-type semiconductor layer, l-type semiconductor layer, and n-type semiconductor layer in the present invention will be described in detail.

At least the l-type semiconductor layer of the photovoltaic device of the present invention includes Zn5e:H@ or Zn5el according to the present invention described above.
-1lTllI+c: Hll is preferably used. This point will be further clarified by the study results described below.

That is, Zn3%Zn5a, which has a relatively large band gap, has conventionally been used as a semiconductor material for photoelectrically converting the high optical energy of short wavelength light.

1-Violet-Vl group compound semiconductors such as ZnTe, CdS, and CdSe%ZnO have been attracting attention. However, most of them are deposited film formation methods that are generally adopted, for example, Z n S % Z n S @ s Cd S
With 5CdSe%ZnO, an n-type semiconductor layer can be easily obtained and the electrical properties are relatively good.
With CdTe, a p-type semiconductor layer can be easily obtained and the electrical properties are relatively good, but in both cases it has been difficult to obtain an i-type semiconductor with excellent electrical properties. Also, the same 1! It has also been difficult to obtain good p-type and n-type semiconductors using -■ group compound semiconductors. Furthermore, especially when it comes to p-type semiconductors with sufficiently wide band gaps.

It was even more difficult to obtain.

The present inventors have developed l-type Zn5e or ZnS@+-8Tex semiconductor films deposited by commonly employed methods, and l-type Zn5e diH or Z
n S e l -II T ell: H semiconductor l
1l (Habo X = 0.8) and others (pin junctions using On-type and P-type semiconductor films were tried, and evaluation as a photovoltaic device was performed based on adhesion and open circuit voltage (Voc).Furthermore, In addition to the l-type semiconductor layer, the p-type and/or n-type semiconductor film is made of Zn5e:H or Zn5al-xT according to the present invention.
The effect of using an ax:H semiconductor film was also evaluated using the same method.

The layer structure of the photovoltaic element was as shown in Figure 1 (B), with the support being quartz glass, the transparent electrode being ITOli formed by sputtering, and the lower electrode being formed by electron beam heating. An Ag thin film was used. n-type, Z
n S e, Z n S.

ZnO, CdS, CdSe semiconductor film and p
The type ZnTe%CdTe semiconductor film was formed by a sputtering method. The dopants for each semiconductor film were those shown in Tables 4 (A) and (B).

The results of the above evaluation are shown in Tables 344 (A) and (B).

From the results in Tables 6 (A) and (8), it is clear that the i-type Zn5e semiconductor film and the n-type Zn5e semiconductor film as II-Vl group compound semiconductors
In the case of pin junction photovoltaic elements using 5e, -1lTel+semiconductor films, although there are some combinations that can be used practically, most of them cannot be used practically. i-type Zn5e:H film and i-type Zn
5e, -1lTell: pin of the present invention using HM
It can be seen that in the case of a junction type photovoltaic device, excellent film adhesion and a large open circuit voltage value can be obtained.

Furthermore, p-type Zn5e:) (two MpHll and/or n-type Zn5e:H:Mp film or p-type Zn5e+-
1lTe, : H:Mp film and/or n-type Zn5e+
-1lTell: It can be seen that the best results can be obtained with the pin junction type photovoltaic device of the present invention using Mn1i.

Based on the above study results, Zn5s provided in the present invention
:811% and Zn5e, -, Te, I: HM has excellent electrical and mechanical properties, and is a photovoltaic material with high photoelectric conversion efficiency for short wavelength light by pin junction, which is the object of the present invention. It was found that this is the most suitable material for the semiconductor layer of the device.

In the present invention, as a means for forming a good pin junction, it is desirable that the formation of an n-type semiconductor layer, the formation of an n-type semiconductor layer, and the formation of a p-type semiconductor layer are performed in succession.
Specifically, if the layers are formed successively in the same deposited film forming apparatus, or if each layer is formed using different apparatuses, the deposited film forming apparatuses are connected via a gate valve, For example, after forming an n-type semiconductor layer in one deposited film forming apparatus, the substrate on which the n-type semiconductor layer has been formed is transferred to another deposited film forming apparatus under vacuum conditions, and then transferred to another deposited film forming apparatus. A type semiconductor is formed, and then the substrate on which the mouth type semiconductor layer and the n type semiconductor layer are laminated is transferred to another deposition forming apparatus under vacuum conditions, and a p type semiconductor is formed in the deposited film forming apparatus. good.

By the way, the above-mentioned Zn5e:H film, Z
n Se1-xTe, :H film, p-type or n-type Zn5
a:H:Mli and p-type or n-type Zn5el-, Te
1l:H:Mli can also be efficiently formed by any of the following three methods.

That is, (1) Raw material gas containing Se atoms and hydrogen gas (H2)
Alternatively, a raw material gas containing Te atoms is introduced into a separate activation region independent from the film forming chamber, and activation energy is applied to these gases to generate excited speciation to form a Se-containing precursor (precursor). A precursor containing atomic hydrogen radicals or further Te is generated, a gas containing the generated precursors and hydrogen radicals is introduced into a film forming chamber, and at the same time, a source gas containing Zn atoms is introduced. is introduced into the film-forming chamber, and both gases are caused to chemically react with each other in a reaction space that is located in the film-forming chamber and dominates the temperature-controlled substrate surface, thereby forming Zn5e:H or Zn5.
el-IITe: A method of forming a functional deposited film composed of H.

(2) Source gas containing Se atoms and hydrogen gas (
H7) and introducing a source gas containing a source gas containing Zn atoms or further Te atoms, and applying high frequency power to a cathode electrode installed in the film forming chamber to form plasma in the reaction space, A method of forming a functional deposited film composed of Zn5e:H or Zn5e+-xTe:H by decomposing, polymerizing, radicalizing, ionizing, etc. the gas introduced therein and causing chemical interaction.

(3) A substrate is placed in a film forming chamber, a cathode electrode is placed at a position facing the substrate and leaving a predetermined space between the substrate, and polycrystalline Zn5 as a target is placed on the surface of the cathode electrode.
Ar gas and H2 gas are introduced into a film forming chamber in which the polycrystalline Zn5e or polycrystalline ZnS e , -1lTe is arranged, and a high frequency voltage is applied to the cathode electrode to form the polycrystalline Zn5e or polycrystalline Zn5e + -, Te. , and at the same time forming a plasma atmosphere in the space, atomic Se and Zn or further Te and H2 gas are excited by the plasma and turned into atomic hydrogen thereby flying out from the target. chemically interact in the space near the surface of the substrate to form Zn5a:H or Zn5a.
A method of forming a functional deposited film composed of 5e+-xTe, :H.

It is of course possible to make the functional deposited films (1) to (3) above have semiconductor properties by containing dopants, and in particular, the p-type dopant can be made from Zn5e:HI.
Il or ZnS e , -1lT e , :H
Zn5e:H:MpHi and Zn5e, which have p-type conductivity, can be contained in
5a, -IITa,: H: It is possible to provide an Mp film. In that case, the purpose can be achieved by introducing a gas containing a p-type dopant into the film forming chamber together with the source gas or hydrogen gas, or independently. Of course, Zn5e:Hlli or Zn5e(-IITen) according to the present invention
When :H[ is made into an n-type material, by using a gas containing an n-type dopant, the dopant can be introduced in the same way as with the p-type material.

The details of the methods (1) to (3) of the present invention will be explained below.

The raw material for introducing Zn in Methods 1 and 2 (hereinafter referred to as "raw material A") is represented by the general formula: R-Zn (where R represents an alkyl residue having 1 to 4 carbon atoms). , alkylzinc compounds that can be easily gasified are preferably used. Specific examples of these alkylzinc compounds include dimethylzinc (DMZ
n), diethylzinc (DEZn) can be mentioned as a representative example. Since these organic zinc compounds are in a liquid state at room temperature, when they are used, they are gasified by bubbling with an inert gas such as Ar or He as a carrier gas.

In addition, as raw materials for introducing Se, gaseous or gasifiable hydrogen selenide (H2Se), halogenated selenium,
Preferred examples include alkyl selenium compounds represented by the general formula R'-3s (where R' represents an alkyl residue having 1 to 4 carbon atoms). and,
Preferred specific examples of the halogenated selenium include selenium hexafluoride, and preferred specific examples of the alkyl selenium compounds include dimethyl selenium (oMse) and diethyl selenium (D
ESe).

In addition, as raw materials for introducing Te, gaseous or gasifiable hydrogen terel (H2Te), halogenated terel,
Suitable examples include alkylterel compounds represented by the general formula R"-Te (where R' represents an alkyl residue having 1 to 4 carbon atoms).
Preferred specific examples of the halogenated terel include terel hexafluoride, and preferred specific examples of the alkyl terel compound include diethyl selenium (DMTe) and diethyl selenium (D
ETe), etc. can be mentioned. (hereinafter Se
The combination of the raw material for introduction and the raw material for Te introduction will be referred to as "raw material B". ) Among these raw materials B, those that are not gaseous but in a liquid or solid state at room temperature may be processed by bubbling, heating sublimation, etc. using an inert gas such as Ar or He or H gas as a carrier gas. and gasify it.

By the method (1) or (2) of the present invention, the above-mentioned Zn
5e:Hill and Zn5el-++Tax:H2 gas is actively used to obtain H films.

By the way, in a preferred embodiment of the method (1) of the present invention, H2 gas is introduced into the activation region together with the gaseous raw material B, and activation energy is applied to make them into excited species. When the raw material B is not gaseous, the activation region is configured to gasify the raw material B using the above-mentioned inert gas or H, gas, and to make the generated gas into excited species. I can do it.

In the method (1) of the present invention, it is of course possible to introduce only the %H2 gas into an activation zone separate from the activation zone to generate excited species.

As the activation energy, discharge energy, thermal energy, light energy, etc. can be used as appropriate, and these energies may be used in combination.

However, the excited speciation of the raw material B can be carried out not only by using active energy but also by using an appropriate catalyst.

By the method (1) or (2) of the present invention, p-type or n-type Zn5e:H:Mllll and p-type or n-type Z
n5e+-, Tl! III: H: In forming the M film, a raw material that provides a gaseous p-type or n-type dopant (hereinafter referred to as "rp-type or n-type dopant raw material") is replaced with a gaseous raw material A or a gaseous raw material This can be achieved by introducing the raw material B into the film forming chamber together with the raw material B, together with the H2 gas, or independently.

As the p-type dopant raw material, a gaseous or easily gasifiable compound is preferably used. Examples of these include propyl lithium (LIC38
? ), secondary butyllithium [L i (see
Suitable examples include organic lithium compounds such as -C,H, )], lithium sulfide compounds (Li2S) that are solid at room temperature, and inorganic lithium compounds such as lithium nitride (Li, N). In addition to these, AsH, PH,
, P2 H4, AsF3. AsC15, PF55
PFs, PCl5.5bHa, 5bFs, etc. can also be cited as suitable examples.

As the n-type dopant raw material, like the above-mentioned p-type dopant raw material, a gas that is a gas at room temperature is appropriately selected from among gases that are easily gasified according to the purpose.

Specifically, for example, trimethylaluminum [Ax
(CH3)s], triethylaluminum [Aj!
(Cm Hs) s], trimethylgallium [
Ga(CH3)s], triethylgallium G
a(caos)sl, trimethylindium [In(
CHs)sl, triethylindium [I n (C*
Hs Ls], diporane (BJa), monosilane (SiH4), disilane (S, iJs), monogermane (GeH4), tin hydride (SnH<), methane (CH4)1, ethane (C2Ha), ethylene (C*
Ha), acetylene (C2H,), fluorine (p”t
)-chlorine (Cj!2) and the like can be mentioned as suitable raw materials.

When using a material that is liquid at room temperature as a p-type or n-type dopant raw material, as described in the raw material A or raw material B, an inert gas such as Ar%He or H gas is used as a carrier gas. Use by bubbling and gasifying. In addition, in the case of a substance that is solid at room temperature, a heating sublimation furnace is prepared, and a carrier gas such as Ar%1(e) is used in the furnace to gasify it by heating and sublimation.

p-type or n-type Zn5e:H:M film or p-type or n
The above (1
), gaseous raw materials B and H2
It is more effective to introduce the dopant raw material together with the gas into the activation region to generate excited species.

By the methods (1) and (2) of the present invention, Zn5e
:Hg% p-type or n-type Zn5e:H:M film, Zn5el
-x Te,: H film and p-type or n-type Z n S
e, l +ll T ax : H: When manufacturing Mli, the substrate temperature is preferably 50 to 60
0°C, more preferably 50-500°C, optimally 100°C
The film forming operation is carried out by adjusting the temperature to ~400°C. In any case, when the substrate temperature is in the range of 50 to 600°C, crystal grains and non-crystal grain regions may be separated, especially when film formation is performed by changing the amount of hydrogen radicals or the amount of H gas droplets. Generally, a deposited film containing a mixture of

One of the other film forming conditions in the methods (1) and (2) is the internal pressure during the forming III operation.

That is, the internal pressure is preferably between txto-' and 50 Torr.
, more preferably 5 x 10'' to 10 Torr, optimally set to 1 x 10'' to 5 Torr.Furthermore, gaseous raw material A1 gaseous raw material B1 hydrogen gas, gaseous p-type dopant. The raw material is introduced into the deposition chamber while its flow rate is controlled by a mass flow controller so as to match the predetermined deposition droplet volume conditions for the film to be manufactured, and the interior of the deposition chamber is evacuated to maintain the internal pressure.

In the method (1) of the present invention, the ratio between the total flow rate of gaseous raw material A and gaseous raw material B introduced into the film forming chamber and the amount of atomic hydrogen radicals is as follows: raw material A, raw material B type of,
It is determined as appropriate depending on the desired characteristics of the functional deposited film, etc., but it is preferably 1:10 to 1:10', more preferably 1:25 to 1:10''.

In the method (2) of the present invention, the ratio between the total flow rate of gaseous raw material A and gaseous raw material B and the hydrogen gas flow rate is determined by the applied high frequency power, the internal pressure, and the hydrogen contained in the deposited film. It is determined appropriately depending on the amount and correlation, etc., but preferably 1:
20 to 1:5 x 10', more preferably 1:30 to 1:5
X10'.

This method, as described above, uses the above-mentioned Zn5e:HIII% p-type or n-type Z
n5a:H:M film, ZnSel-++T
eX:HII! , or p-type or n-type Z n S e
l -X T e II: H: Mll! This is a method of manufacturing.

The target is typically polycrystalline Zn5e or polycrystalline ZnSel-xTe with a desired Se to Te content ratio.
, is used. In addition, two targets of Zn%Se or two targets of Zn5e and ZnTe may be used. In a preferred embodiment when sputtering targets using high frequency power, H2 gas and Ar gas or/and A gas atmosphere containing He gas is formed, and the process is carried out in this atmosphere.

By the method (3) of the present invention, p-type or n-type Zn5e
:H: MIli, or p-type or n-type Zn5el-, T
When producing e,:H:Mlli, a predetermined amount of the gaseous p-type or n-type dopant raw material described in method (1) or (2) is mixed in the gas atmosphere and the sputtering is performed. to form a film.

Desired Zn5e:H by the method (3) of the present invention
membrane, p-type or n1MZn5e:H:M membrane, ZnS
e +-8Ta, :H film or p-type or n-type Zn5e
+-++ In manufacturing the Te, :H:M film,
distance between target and substrate, high frequency power, substrate temperature,
Film forming conditions related to internal pressure and gas flow rate are important. First, the distance between the target and the substrate depends on the configuration of the equipment used,
It varies somewhat depending on the scale, but in general, preferably 20
~1o.

(2) The optimum value is 40 to 80III11. The high frequency power will vary depending on the type and size of the target, but in general, it is preferably 0.3 to 7
W/cm2, optimally 0.8 to 4 W/am'.

The substrate temperature is set in the same temperature range as in method (1) or (2) above. Further, the internal pressure during film formation is preferably lXl0-' to 1x10-'Tor
r, more preferably 1xlO-' to lx10-'Tor
It is r. Furthermore, regarding H2 gas, Ar gas or/and He gas, and p-type dopant raw material, in relation to the amount of atomic Zn and Se that fly out by sputtering the target, or the amount of Te, in the reaction zone of the film forming chamber. The film is formed while being controlled by a mass flow controller so that the gas atmosphere meets preset film forming conditions such that it contains a predetermined amount of hydrogen atoms (H) or hydrogen atoms (H) and dopant (M) (i.e., H+M). The film is introduced into the film forming chamber, and the film forming chamber is evacuated while maintaining the internal pressure. That is,
In the present invention, the production ratio of the total amount of atomic Zn and Se or the total amount of atomic Zn, Sa, and Te and hydrogen atoms (H) or hydrogen atoms (H) and dopant (M) (i.e., H+M) is , preferably 1021 to 1:10', more preferably 10:1 to 1:102. Optimally 5:1 to 1:5
It is desirable to set it to 0.

As described above, the method of the present invention can be carried out using appropriate apparatuses, and the apparatuses shown in FIGS. 2 to 4 are representative examples of such apparatuses.

That is, first, FIG. 2 is a schematic diagram of an example of a deposited film forming apparatus suitable for carrying out the method (1) of the present invention. Substrate cassette 202 placed in film forming chamber 201
A substrate 203 is fixed on top. The substrate 203 is monitored by a temperature monitor 204 and heated by an infrared heater 20.
5, it is radiantly heated. The substrate cassette 202 is transported by a substrate transport device 206 to another film forming chamber 213 or a load rotor chamber 212 via a gate valve 207 . A source gas (A) is introduced into the film forming chamber 201 from a gas introduction pipe (A) 208 . Raw material gas (B) and hydrogen gas are introduced from the gas introduction pipe (B) 209, and are introduced into the activation chamber 210.
Activated by the activation means 211 in the film forming chamber 2
01. Here, the activation means means that the raw material gas (A
) and raw material gas (B) and hydrogen gas are decomposed, polymerized, radicalized, ionized, etc., to produce raw material gas (A) and raw material gas (B).
) and hydrogen gas, or means to promote the reaction on the substrate surface.

Further, the gas inside the film forming chamber is exhausted by an exhaust pump 215 via a valve 214, and the inside of the film forming chamber is maintained at a predetermined pressure.

Zn5e of the present invention using the apparatus of FIG. 2: Hll
An example of manufacturing i will be explained.

First, S such as DESe introduced from the gas introduction pipe 209
The raw material gas (B) containing s and hydrogen gas are in the activation chamber 21.
0, the precursor is activated by the activation energy applied by the activation means 211, and a Se-containing precursor and atomic hydrogen radicals are formed.

On the other hand, the raw material gas (A) containing Zn such as DEZn introduced from another gas introduction pipe 208 is
Since the discharge port from the activation chamber 210 is located downstream from the activation chamber 210, the activation means does not pre-excite the
The gas is introduced into the film forming chamber 201 from the outlet of the gas introduction pipe 208 . Raw material gas (A) containing Zn in the film forming chamber
causes a chemical reaction with H radicals and becomes a precursor containing Zn.

In this way, the Se-containing precursor introduced into the film forming chamber,
The precursor containing Zn and hydrogen radicals undergo chemical interaction in the film forming chamber to form Zn5e with the desired hydrogen content.
: Forms Ha.

Hydrogen radicals are also thought to be involved in the film deposition reaction on the substrate surface, and have the effect of removing unnecessary alkyl groups from the deposited film and acting as terminators to fill the dangling bonds in the Zn5e thin film. and becomes incorporated into the membrane. Also, Zn in the reaction chamber
In order to increase the reaction between the raw material gas containing Zn and the hydrogen radicals, the reaction between the Zn-containing precursor and the Se-containing precursor, and the supply amount of hydrogen radicals, the amount of energy provided by the activation means may be increased as necessary. It is also possible to draw out the activation energy in the activation chamber into the film forming chamber by increasing the activation energy. The amount of hydrogen atoms (H) contained in the Zn5e:H film depends on the flow rate of hydrogen gas introduced as a source gas, the amount of activation energy applied, the pressure inside the deposition chamber, and the opening facing the deposition chamber. This can be controlled by setting the distance between the gas discharge port of the gas introduction pipe 208 and the activation chamber 210 and the substrate temperature to desired values. Further, in order to control the conductivity type, the above-mentioned dopant raw material may be added to the raw material gas (A) or the raw material gas (B).

Further, FIG. 3 is a schematic diagram of an example of a deposited film forming apparatus suitable for carrying out the method (2) of the present invention.
In this device, the raw material gas (A) is supplied to the gas inlet pipe (A) 3.
08, the raw material gas (B) and hydrogen gas are introduced from the gas introduction pipe (B) 309 and mixed, and then the high frequency power source 3
In the plasma generated by high frequency power applied to the cathode electrode 312 from 10 through circuit matching,
It reacts by decomposition, polymerization, radicalization, ionization, etc., and forms a Zn5e:Hf1l film or Zn5e, -, on the substrate 303.
A Te,:H thin film is deposited. Furthermore, by adding and flowing the above-mentioned dopant raw material, a p-type or n-type doped deposited film can be obtained.

Further, FIG. 4 is a schematic diagram of an example of a deposited film forming apparatus suitable for carrying out the method (3) of the present invention. In this device, Zn5e is deposited on the cathode electrode 412.
Polycrystalline or Zn5el-11T with desired Se to Te amount ratio
Polycrystalline targets 413 of e and l are bonded together, and
Ar gas and H2 gas are introduced from the gas inlet 408, and the target 413 is sputtered by the Ar and H ions generated in the plasma generated by the high frequency power applied to the cathode electrode, and Z is formed on the substrate 403.
n5e: Hlli or Z n S e l-x T e
, :Hlli is deposited. Also, Ar gas and H
By introducing a mixture of the above-mentioned dopant materials into the gas, a p-type or n-type doped deposited film can be obtained.

[Examples] The photovoltaic device of the present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples in any way.

Example 1 The pin-type junction photovoltaic device shown in FIG. 1(A) was manufactured using the stack #tLIII forming apparatus shown in FIG. 2 according to the method (1) of the present invention described above in accordance with the following procedure.

A stainless steel substrate 101 with a size of 50 mm x 50 mm was placed in a sputtering device (not shown) and sputtered 10-'.
After evacuation to Torr or less, Ag is sputtered onto the substrate as a lower electrode 102 with about 1000 A
g electrode was deposited. This substrate is taken out and fixed to the substrate cassette 202 on the substrate transfer device 206 in the load lock chamber 212 with the side on which the lower electrode 102 is deposited facing downward in the figure. The pressure was evacuated to 10-' Torr or less using an exhaust pump. During this time, the film forming chamber 201 is operated by the exhaust pump 215.
When the pressures of the six compartments, which are evacuated to pressures below Torr, become almost equal, the substrate transfer device 206 is opened.
Moved to 11m201.

Next, the substrate was heated using an infrared heater 205 so that the substrate temperature reached 200°C. While controlling the Ar gas stored in the gas cylinder 217 by the mass flow controller 219, it is introduced at a flow rate of 155 CCM into DESa in a liquid state stored in the dewar bin 223 for bubbling, and the Ar gas is saturated with % DESa.
r gas and H2 gas stored in the gas cylinder 216,
155CCM by mass flow controller 218
The gas was introduced into the gas introduction pipe 209 while being controlled so as to be controlled as follows. The flow rate of DESe introduced was 1.5 x 10-'+ol/sin
Then, the DEZn stored in the Dewarbin 224 was reduced to t, oxto-'mol by the same procedure as described above.
At a flow rate of 1/1 inch, TEAJ2 stored in the dewar bin 225 was further heated in the same manner as described above.
, Ox was introduced into the gas introduction tube 208 at a flow rate of 10-'' mol/min. At this time, the flow rate of the carrier gas Ar was 55 CCM, respectively.

The amounts of DESa, DEZn, and TEAjl introduced were determined by the dewar bottle 223,224,225 that stored each liquid.
The temperature of the constant temperature water in constant temperature water tanks 227, 228 and 227 placed outside of the was controlled by a heater, and the temperature of each raw material liquid was adjusted. In addition, 228~
230 is constant temperature water for temperature control, and 231 to 233 are heaters.

Next, adjust the opening degree of the exhaust valve 214, and
The internal pressure of 1 was maintained at 0.5 Torr. then 2450
Microwave power of 200 W was inputted from the MHz microwave generator 2211, and film formation was started. N-type Zn5e: H: Aj! with 2 minutes of film formation. Il! After forming N203, the input of microwave power was stopped, and at the same time, the introduction of gas was also stopped, and the vacuum pump 215 was used to remove the film N201 by 10-
'Evacuated to below Torr. Next: Using exactly the same method and procedure as above, except that the introduction of jEAIL was stopped, n
Type Zn5e: H: l type Z on AJ2111103
n5e: H3i104 was deposited. The film forming time was 50 minutes.

Next, LiC5Hy stored in the Dewarbin 224 as a raw material gas is mixed with 1 Ox 10-' mol/a+
P-type Zn5e:H:Lifll 105 was formed on n-type Zn5e:H@103 by the same method and procedure as described above, except that the gas was introduced from the gas introduction pipe 208 at the in-line temperature.

Table 7 summarizes the film forming conditions of 0 or more in which the film forming time was 20 minutes.

Table 7: Manufacturing conditions for Zn5e:H(:M)III (Manufacturing method 1) After film formation, the substrate transfer device 206 is moved to the load lock chamber 212 via the gate pulp 207, and after cooling, the n-type and i-type Then, the substrate on which the p-type semiconductor layer was deposited was taken out. The substrate is placed in a vacuum evaporation device, and I O-'T
After evacuation to below orr, In and Sn metal pieces were placed in a crucible at a weight ratio of 1:1, and I was heated by resistance heating.
Approximately 100 people deposited an ITO thin film in an oxygen atmosphere of about X 10-'Torr to form a transparent electrode 106. The substrate temperature at this time was 175°C. After cooling, the substrate is taken out, a permalloy mask is placed on the top surface of the transparent electrode 106,
Sample No. 1 was placed in a vacuum evaporation apparatus, evacuated to a pressure of 1 x 10-' Torr or less, and then Ag was evaporated to a thickness of about 1.0 μm by resistance heating to form a comb-shaped current collecting electrode 107.

It was set to 1.

The characteristics of this sample No. 1 were evaluated as follows.

AM-1 light (10
0 mw/am2), and the open circuit voltage Voc, AM-
The output when one light was irradiated through a 4001 m interference filter, and the change Δ in conversion efficiency before and after irradiation by irradiating AM-1 light for 10 hours were measured. The measurement results are shown in Table 16.

Separately, s i02 III formed by thermal oxidation on Si single crystal die and a quartz glass substrate were prepared, and an n-type semiconductor layer was formed on each surface using the same method and procedure as described above. Zn5e:H:AJ! Il
l, Zn5e:H film as n-type semiconductor layer and Zn5e as p-type semiconductor layer:)i:Li1l! were formed individually. Regarding the obtained deposited film, the hydrogen atom content and the ratio of crystal grain regions in the film were measured according to the method described above. The measurement results are shown in Table 16.

Next, using the film forming apparatus shown in FIG.
2) with the structure shown in FIG. 1(A)
An n-junction photovoltaic device was fabricated. A lower electrode 10 was formed on a stainless steel substrate 101 in the same manner as in Example 1.
2, a substrate cassette 302 has a thin Ag film deposited on it.
The substrate 303 is heated to 300°C using an infrared heater 305 while keeping the internal pressure of the film forming chamber 301 below 10-'Torr.
Raw material gas A and raw material gas B were heated to
It was introduced into room I 301.

The internal pressure of the growth chamber 301 was maintained at 1.0 Torr by adjusting the opening of the exhaust valve 314. A high frequency power source 310 is connected to a cathode electrode 312 via a matching circuit 311, and a frequency of 13.56 MHz is generated from the high frequency power source 310.
A high frequency power of 50 W was immediately applied to start film formation.

After 2 minutes of discharge, n-type Zn5e: H: A
j! After forming the film 103, the high frequency power source was switched off and the introduction of gas was also stopped. The internal pressure of the deposition chamber was set to 10-'Torr.
After vacuum evacuation, the raw material gas A shown in Table 8 again,
B was introduced into the film forming chamber 301.

While maintaining the internal pressure at 1.0 Torr, high frequency power of 50 W was applied from the high frequency power supply 310 and discharge was performed for 50 minutes.
Type Zn5e: H: i type Zn5e on A41wA103
: H film 104 was formed. After that, the same procedure was repeated for 2 minutes of discharge under the conditions shown in Table 8 to produce n-type Zn5e:
P-type Z n S e : H : L on the H film 104
i lli 105 was formed.

Table 8 Manufacturing conditions for Zn5e:H (:M) film (Manufacturing method 2) After film formation, take it out from the film formation chamber and use the same method as shown in Example 1 to form a transparent electrode 106! Approximately 700 people formed a film of TOIII, and an Ag thin film was formed thereon as a current collecting electrode 107 to form a sample N002, and the solar cell characteristics were evaluated.

The evaluation results are shown in Table 16.

Separately, 5iozfl! formed on a Si wafer!
and quartz substrates were prepared, and each layer of Zn5e :H.(:M)IIi was deposited on each surface in the same manner as above. For each of the obtained deposited films, the hydrogen atom content and the ratio of crystal grain regions in the film were measured in the same manner as in Example 1. The measurement results are shown in Table 16.

Example 3 Next, (3) of the present invention described above was carried out using the apparatus shown in FIG.
A pin-coupled photovoltaic device having the structure shown in FIG. 1(A) was manufactured using the manufacturing method described above.

A substrate on which an Ag lower electrode 102 is deposited on a stainless steel substrate 101 in the same manner as in the method and procedure shown in Example 1 is fixed to a substrate cassette 402 and transported into a film forming chamber 401. It was kept below 10-' Torr. A Zn5e polycrystalline target 416 was placed on the cathode electrode 412. The substrate 403 is connected to the infrared heater 40
5, using the raw material gas shown in Table 9, and under the conditions shown in the table, the gas inlet pipe 408 h
% was introduced into the film forming chamber 401. The opening degree of the exhaust valve 414 was adjusted to maintain the internal pressure of the film forming chamber 401 at 0.05 Torr, and high frequency power of 300 W was applied to start film forming. 3
After a minute of discharge, n-type Zn5e:H:Aflli103
was formed, the discharge was stopped, and the introduction of gas was also stopped.

Next, the film forming chamber was evacuated to 10-'Torr or less, and the raw material gases shown in Table 9 were introduced under the conditions shown in the table, and a film was formed for 60 minutes at a pressure of 0.5 Torr and a discharge power of 300 W. i-type Z n S e : Hlli 104 was formed.

Table 9 Manufacturing conditions for Zn5e:H(:M)lli (Manufacturing method 3) Thereafter, a p-type film was formed on the n-type Zn5e:H film 104 by discharging for 3 minutes using the same procedure again under the conditions shown in Table 9. Zn5e:H:Li1il105 was formed.

After the film formation, an ITO film 70 is placed on the sample as a transparent electrode 106.
An Ag film was deposited as the current collecting electrode 107 for the sample N0.
As No. 03, characteristics evaluation as a solar cell was conducted. The evaluation results are shown in Table 16.

Separately, a 5iC)2 film formed on a Si wafer and a quartz substrate were prepared, and each layer of Zn5e:H(:M) film was deposited on each surface in the same manner as above. For each of the deposited films obtained, the hydrogen atom content and the ratio of crystalline regions in the film were measured in the same manner as in Example 1.

The measurement results are shown in Table 16.

fruit! (A) In the method for manufacturing the photovoltaic device shown in Examples 1 to 3, the p-type, n-type, and n-type Zn5e :H (:M) films are formed using the same film-forming chamber. However, the p-type, n-type, and n-type semiconductor layers may be manufactured by different manufacturing methods.

Examples of manufacturing a pin junction photovoltaic device in which the methods for manufacturing the p-type and n-type semiconductor layers and the method for manufacturing the n-type semiconductor layer are different will be described below.

First, a lower electrode 102 of Ag is placed on a stainless steel substrate 101.
The substrate on which 3,000 films were deposited is placed in the substrate cassette 30 in Figure 3.
2, and n-type Zn5e:H:Au1i103 was deposited using the method and procedure shown in Example 2. After deposition,
The film forming chamber was evacuated to 10 −5 τ orr or less, and the substrate transfer device 306 was moved to the second film forming chamber 316 via the gate valve 307 . Here, a deposited film forming apparatus shown in FIG. 2 is connected to the second film forming chamber 316 via a gate valve 307. Subsequently, in the same manner as shown in Example 1, type l Z n S e : HIll 104
n-type Zn5e: H:Af! , were successively formed on Ill.

Furthermore, the substrate transfer device 30 is transferred again via the gate valve 307.
6 was returned to the first film forming chamber, and a p-type Zn5a:H:Li film 105 was deposited using the method and procedure shown in Example 2. The p-type Zn5e:H:Li1 thus formed
A transparent electrode 106 made of an ITO film and a current collecting electrode 107 made of Ag were deposited on Li in the same manner as in Example 1, and characteristics were evaluated as sample N014. 17th evaluation result
Shown in the table.

Separately, a SiO□ film formed on a St wafer and a quartz substrate were prepared, and each layer of Zn5e:H(,M)[ was deposited on the surface of each in the same manner as above. For each of the deposited films obtained, the hydrogen atom content and the ratio of crystalline regions in the film were measured in the same manner as in Example 1. The measurement results are shown in Table 17.

Okisori j ZnS:Afllli as the n-type semiconductor layer, Zn5e:Hlli as the n-type semiconductor layer, and Zn5e:H:Lit as the p-type semiconductor layer! ! In this example, the functional deposition method of the present invention was used as the method for forming an n-type ZnS:AfL film. A method similar to the membrane manufacturing methods (1) to (3) is used, and the following 10th method is used.
The formation was performed under manufacturing conditions 4 to 6 shown in the table.

Table 10 = Fabrication conditions for n-type ZnS:AItIli By the same operation as in Example 1, fabrication methods 4 to 6 in Table 10 described above were applied on a stainless steel substrate on which an Ag electrode as a lower electrode was deposited. n-type ZnS:A as an n-type semiconductor layer
1MZn5e was deposited on the n-type ZnS:AJ2Ili in the same manner as in Examples 1 to 3.
:H film and p-type Zn5e:H:LiM were stacked to form a semiconductor layer having a pin junction. In this way the 18th
A semiconductor layer having the pin junction shown in the table was formed, and then a transparent electrode 106 and a current collecting electrode 107 were deposited in the same manner as in Example 1, and samples Nos. 5 to 13 were used as photovoltaic devices. Characteristic evaluations similar to those in Example 1 were performed. The evaluation results are shown in Table 18.

Separately, s i 02I formed on a St wafer
II and a quartz substrate were prepared, and each layer of Zn5e:H:(:M) film was deposited on each surface in the same manner as above. For each of the deposited films obtained, the hydrogen atom content and the ratio of crystalline regions in the film were measured in the same manner as in Example 1. The measurement results are shown in Table 18.

Then, ZnO:Ajlli was formed as an n-type semiconductor layer, i-type Zn5e:HIII was formed as an l-type semiconductor layer, and p-type Zn5e:)I:Li1ll was formed as a p-type semiconductor layer. A pin junction type photovoltaic device having the structure shown in was manufactured.

The n-type ZnO:All film was manufactured in the same manner as in Examples 1 to 3, except that the manufacturing conditions were as shown in Table 11 below.

Table 11: Fabrication conditions for n-type ZnO:AJR Under the fabrication conditions shown in Table 11 above, an n-type ZnO:AILlli film was formed on an Ag electrode formed by vapor deposition on a stainless steel substrate, and then this n-type An i-type Zn5e:H film and a p-type Zn5e:H:Li1lii film were formed on the ZnO:AJ2 film 103 according to the manufacturing conditions and procedures shown in Examples 1 to 3. After that, this p-type Zn5e:H:Li1l
On i! T011i and Ag current collecting electrode were sequentially laminated.

According to such a procedure, pln junction type photovoltaic elements (sample Nos. 14 to 22) were produced.

Table 19 shows the evaluation results obtained by measuring the characteristics of these samples.

Separately, S L Ot formed on Sll sea urchin
A and a quartz substrate were prepared, and Zn5e:H: (:M) film was deposited on each surface in the same manner as above. For each of the deposited films obtained, the hydrogen atom content and the ratio of crystalline regions in the film were measured in the same manner as in Example 1. The measurement results are shown in Table 19.

A Zn5e:All film was used as the JCI un-type semiconductor layer, a Zn5e:H film was used as the l-type semiconductor layer, and a p-type semiconductor layer was used as the p-type semiconductor layer.
A βin junction type photovoltaic device having the structure shown in FIG. 1(A) was manufactured by forming 1llll of Zn5a:H:Li1, respectively. N-type Zn5e:Aj2111 was produced in the same manner as in Examples 1 to 3, except that the production conditions were as shown in Table 12 below.

Table 12: Conditions for manufacturing n-type Zn5e:All film This first
Under the manufacturing conditions shown in Table 2, n-type Zn5e:A4111 was deposited on an Ag electrode formed by vaporization on a stainless steel substrate.
%, and then this n-type Zn5e:AJ2 film 10
3, n-type Zn5e:Hlli and p-type Zn5e:H:
A film of Li1li was formed.

After that, ITOl was deposited on this p-type Zn5e:H:Li film.
Li and Ag current collecting electrodes were sequentially laminated.

According to such a procedure, %P in junction type photovoltaic devices (sample Nos. 23 to 31) were produced.

Table 20 shows the evaluation results obtained by measuring the characteristics of these samples.

Separately, the 5tO2 film formed on the St urchin bar and the quartz substrate were prepared, and each layer of Zn5e:H:(:M) film was deposited on each surface in the same manner as above. For each of the deposited films obtained, the hydrogen atom content and the ratio of crystalline regions in the film were measured in the same manner as in Example 1. The measurement results are shown in Table 20.

Shigori! A pin junction type light beam having the structure shown in FIG. In this example, a variety of electromotive force elements were manufactured.As a method for forming a p-type ZnTe:Li film, the method for manufacturing a functional deposited film (1) of the present invention was used.
The formation was carried out using a method similar to (3) and under manufacturing conditions 13 to 15 shown in Table 13 below.

By the same operation as in Example 1, A was used as the lower electrode 102.
On the stainless steel substrate on which the g electrode was deposited, an
Type Zn5e:H:AIL@ and l as n-type semiconductor layer
deposit the i-type Zn5e:H1
p-type Z under manufacturing conditions 13 to 15 shown in Table 13 on
nTe: Li1li was stacked to form a semiconductor layer having a pin junction (in this way, as shown in Table 21,
A semiconductor layer having a pin junction was formed, and then a transparent electrode 106 and a current collecting electrode 107 were deposited in the same manner as in Example 1, and samples Nos. 32 to 40 were prepared as Example 1 as a photovoltaic element. Characteristic evaluations similar to those were performed. The evaluation results are shown in Table 21.

Separately, a 5i02 film formed on a Si wafer and a quartz substrate were prepared, and each layer of Zn5e:H(:M)III was deposited on each surface in the same manner as above. For each of the deposited films obtained, the hydrogen atom content and the ratio of crystalline regions in the film were measured in the same manner as in Example 1.

The measurement results are shown in Table 21.

Table 13: p-type ZnTe: LllI! A pin junction photovoltaic device having the structure shown in FIG. 1(B) was prepared using a glass substrate instead of a stainless steel substrate, and the characteristics were evaluated in the same manner as in Example 1. . The manufacturing method will be described below.

500 people formed an ITO film as a transparent electrode on a Corning #7059 glass substrate 101 by sputtering method, and using this substrate, p-type Zn5e was formed under the same operation and manufacturing conditions as in Example 1. H: Litli and l
A type Zn5e:H film was deposited.

Subsequently, an n-type semiconductor layer 103 was deposited using the manufacturing method shown in Table 14 below.

Table 14) The method for manufacturing the n-type semiconductor layer shown in Examples 1 to 7 is followed.

Next, on the semiconductor layer formed up to the n-type semiconductor layer, an SOO film of Ag was deposited by electron beam evaporation to form the lower electrode 102. These samples were designated as sample N.

41 to 44. The characteristics of each sample as a photovoltaic device were evaluated in the same manner as in Example 1, and the results of 0 or more are summarized in Table 22.

Separately, s i 02 formed on a St wafer
Ill and a quartz substrate were prepared, and each layer of Zn5e:H(·M)Ill was deposited on each surface in the same manner as described above. For each of the deposited films obtained, the hydrogen atom content and the ratio of crystalline regions in the film were measured in the same manner as in Example 1. The measurement results are shown in Table 22.

Separately, p-type ZnTe:Li11 was prepared using the same operations and manufacturing conditions as in Example 8 on a substrate on which ITO was formed.
i was deposited. Subsequently, l-type Zn5e:Hlli and n-type Z
An n5e:H:Ar1 film was deposited.

Next, in the same manner as samples No. 41 to 44, sample No.
No. 45 was obtained, and the characteristics were evaluated in the same manner. 22nd measurement result
Shown in the table.

<Comparative Example 1> In order to see how the photovoltaic device characteristics change depending on the manufacturing conditions of the Zn5e:H film of the n-type semiconductor layer, the Figure 1 (A
) A pin junction type photovoltaic element and an l-type Z
n5e: H grass FlrIA was produced and evaluated in the same manner as in Example 1. The results are sample No.
46-48 in Table 23.

Separately, S i 02 formed on a St wafer
Ill and a quartz substrate were prepared, and each layer of Zn5e:H was applied to the surface of each in the same manner as in Sample No. 46 to 48 above.
(:M) film was deposited. For each of the deposited films obtained, the hydrogen atom content and the ratio of crystalline regions in the film were measured in the same manner as in Example 1. The measurement results are shown in Table 23.

Table 15: I-type Zn5e:H film production conditions Comparative Example 2
Next, a pin-type photovoltaic device of a-5t:H having the structure shown in FIG. 1(C) was produced by the glow discharge method using the apparatus shown in FIG. 3 and the procedure shown below.

About 1000 pieces of Ag were deposited on a stainless steel substrate 101 measuring 50 mm x 50 m+s by sputtering to form an electrode 102 . Thereafter, the substrate was fixed to the substrate cassette 302 with the electrode 102 facing downward, and the internal pressure of the film forming chamber 301 was evacuated to 10'' Torr or less.Heater 30
5 was used to maintain the substrate temperature at 250°C. SiH4 gas, H2 gas, PH, gas (1%
(diluted with H7 to a concentration of 30% each)
5CCIA, 4 Q 5CCIA, 10 SCCM
The gas was introduced from the gas inlet 308 at a flow rate of . Film forming chamber 301
The n-type A-3t:H film 10B was maintained at 0.05 Torr, and the high-frequency power SOW was applied to maintain the discharge for 3 minutes.
was deposited. Thereafter, the high frequency power was stopped, gas introduction was stopped, and the inside of the film forming chamber 301 was evacuated to 10-' Torr or less. Next, 5LH4 gas, H, and gas were pumped into the film forming chamber from each cylinder at a flow rate of 30 SCCM and 40 SCCM, respectively. 30
1 and 0.5 Torr, 70 in the same manner as above.
Discharge with W for 60 minutes, type i A-5i: Hllil
After forming the O9 film, the discharge and gas introduction were stopped, and the inside of the film forming chamber 301 was evacuated to 10-' Torr or less, and 5iHa gas, H gas, B2H gas, and gas (Hz
(diluted to 1% concentration with gas) at 30 SC each.
CM, 200 SCC, M, , 20 SCCM is introduced into the film forming chamber 301, internal pressure Q, 6 Torr, high frequency power S
A p-type A-5t:HIIillo film was formed by discharging for 2 minutes under OW. After the film formation is completed, the sample is taken out and the ITO electrode is
Ten electrodes of E and Ag were formed in the same manner as in Example 1, and a pin junction type A-5i photovoltaic device was produced. The photovoltaic properties of this sample were evaluated, and the results are listed in Table 's23 as sample No.

It was shown as 49.

Table 16 Table 18 Table 20 Table 119 Table 1g 21 Table 22 Table 23 Characteristic evaluation results of each sample> Characteristic evaluation results of each sample according to Examples 1 to 9 and Comparative Example 1.2 It is shown in Table 23.

The characteristics evaluation items as a photovoltaic element include the open-circuit voltage (Voc) under AM-1 light (10Q mw/cm'') irradiation, and the open-circuit voltage (Voc) under AM-1 irradiation transmitted through a 400 nm interference filter. Output relative value (relative value of the output of each electromotive force element to the output of the A-3i pin type photovoltaic element produced in Comparative Example 2 under interference filter transmitted light), AM-1 light continuous 10 The rate of change in photoelectric conversion efficiency before and after time irradiation (Δη/η.; Δη is the amount of change in photoelectric conversion efficiency, and η is the initial photoelectric conversion efficiency) is shown, and these evaluation results are shown. .

In addition, the l-type Zn used to construct each photovoltaic element
Each i-type ZnS@:)l:Li@ was prepared in order to confirm whether the 5e:H:Li film was controlled to the hydrogen atom content and crystal grain area ratio in the film specified in the present invention.
Measurements of the content of hydrogen atoms and the percentage of grain area are shown.

From the above results, in Examples 1 to 4, the pi1 junction photovoltaic device of the present invention was formed on a stainless steel substrate with the content of hydrogen atoms in the film and the ratio of crystal grain area per unit volume set within a specific range. p-type Zn5e:H:Li1i,l
Type Zn5e: Hill and n-type Zn5e: Al11il
was fabricated, and its pin junction was well formed, resulting in a high open circuit voltage (the output under AM-1 light irradiation transmitted through a 400 nm interference filter was the same as that of the conventional A-5i).
It is larger than an n-type photovoltaic element, and has a smaller rate of change in photoelectric conversion efficiency before and after 10 hours of continuous irradiation before AM-1.
In other words, it was found that there was little photodeterioration.

In Example 5, n-type ZnS:AJ was deposited on a stainless steel substrate.
III and l-type Zn5e: H film and p-type Zn5a
: H: A photovoltaic device was produced by depositing Llli and attempting pin junction thereof, and a photovoltaic device having good characteristics as in Examples 1 to 4 was obtained.

In Example 6, n-type ZnO:Al was deposited on a stainless steel substrate.
2 film and l-type Zn5e: H film and p-type Zn5e:H
A photovoltaic device was produced by depositing Lifi and attempting pin-to-pin junctions between them, and a photovoltaic device having good characteristics similar to Examples 1 to 4 was obtained.

In Example 7, n-type Zn5e:A was deposited on a stainless steel substrate.
ll film and l-type Zn5e: lli and p-type Zn5e:
A photovoltaic device was fabricated by depositing H:LiM and trying to form a pin junction between them, and a photovoltaic device having good characteristics similar to Examples 1 to 4 was obtained.

In Example 8, n-type Zn5e:
H: AJ2111 and l-type Zn5e: H1l! A photovoltaic device was fabricated by depositing and p-type ZnTe:Li film and attempting to pin-junction them, and a photovoltaic device having good characteristics as in Examples 1 to 4 was obtained.

In Example 9, the Zn5e:H:
(:M), ZnS:AfL, ZnO:An, and Zn5 were deposited as an n-type semiconductor layer or a p-type semiconductor layer, respectively.
e: AJI, pint using ZnTa:Li! Although the trapezoidal photovoltaic type photovoltaic device was used, one having good characteristics similar to Examples 1 to 8 was obtained.

Comparative Example 1 evaluates the characteristics of a photovoltaic device obtained under conditions in which the amount of H2 gas introduced during the production of the l-type Zn5e:H film was changed in the method for producing a photovoltaic device carried out in Example 1. A comparison was made. Obtained l-type Zn5e:H:L
Both the hydrogen atom content and the ratio of crystal grain regions in i1li deviated from the specified values, and as a result, the electrical properties were also inferior compared to Examples 1 to 9.

In Comparative Example 2, a conventional A-5t pin-type photovoltaic device was prepared as a comparison target for characteristic evaluation of the photovoltaic device of the present invention. was low, and photodegradation was also large.

Riko Oishoko A The above-described method of the present invention (
1) according to the following procedure.

A stainless steel substrate 101 with a size of 50 lIlm x 50 ll1m was placed in a sputtering device (not shown) and evacuated to 10-' Torr or less, and then Ag was sputtered in Ar to form a lower electrode 102 on the substrate with a diameter of about 100 mm.
0 Ag electrodes were deposited. This substrate is taken out and fixed to the substrate cassette 202 on the substrate transfer device 206 in the load lock chamber 212 with the side on which the lower electrode tQ2 is deposited facing downward in the figure. The vacuum was evacuated to a pressure of 10 mm or less using an exhaust pump. During this time, the film forming chamber 201 is opened by the exhaust pump 215 when the pressures in both chambers, which are evacuated to a pressure of 10 Torr or less, become almost equal, and the substrate transfer device 201 is opened.
6 was placed into the film forming chamber 201.

Next, the substrate was heated using an infrared heater 205 so that the substrate temperature reached 200°C. The He gas stored in the gas cylinder 217 is transferred to the mass flow controller 219,
220, bubbling was carried out by introducing DESe and DETe in liquid state stored in dewarbins 223 and 224 at a flow rate of 55 CCM, and saturated with I) E S e , DE Te He gas and H2 gas stored in the gas cylinder 216 are converted to 155C by the mass flow controller 218.
The gas was introduced into the gas introduction pipe 209 while being controlled to CM. The flow rate of introduced DESe was 3.0xlO-'mol/min.
The flow rate of %D E T e is 8 X 10-'mol/
DEZn stored in the Dewarbin 225 was then mixed with 1. Ox10-
'mol/mln flow rate and Dewarn bin 226
TEAIL stored in 3.0X10-”ll1ol
/+in respectively into the gas introduction pipe 208. At this time, the flow rate of the carrier gas He was 55C.
It was made into a commercial.

The amount of each raw material gas introduced is controlled by a constant temperature water tank 227 placed outside the dewar bins 223 to 226 storing each liquid.
It was set by controlling the temperature of constant temperature water in ~230℃ with a heater and adjusting the temperature of each raw material liquid.

In addition, 235-238 are constant temperature water for temperature control, and 231-234 are heaters.

Next, the opening degree of the exhaust valve 214 was adjusted to maintain the internal pressure of the film forming chamber 201 at 0.5 Torr. Then 2450 MH
Microwave power of 200 W was inputted from the microwave generator 211 of Z, and film formation was started. n-type Z after 2 minutes of film formation
n5e, -, Ta,: After forming H:Aλ1li103, the input of microwave power is stopped, and at the same time, the introduction of gas is also stopped, and the formation III chamber 201 is evacuated to 1 by the exhaust pump 215.
n using the same method and procedure as above, except that the introduction of the zero-order TEAf, which was evacuated to below 0-'Torr, was stopped.
Type ZnSel-11Tew:H:
i-type Z n S e + on A I III 103
-x T e X: The H film 104 was formed.

The film forming time was 50 minutes.

Next, 1,,1c3H7 stored in the dewar bin 224 as a raw material gas is
i-type Z n S e l -II using the same method and procedure as above except that the gas was introduced from the gas introduction pipe 208.
A p-type Zn5el-11Tex:H:Li@105 film was formed on Tem:H:A41111103. Table 24 summarizes the film forming conditions of 0 or more in which the film forming time was 20 minutes.

After film formation, the substrate transfer device 206 is connected to the gate valve 207.
After cooling, the n-type
The substrate on which the i-type and p-type semiconductor layers were deposited was taken out.

The substrate was placed in a vacuum evaporation apparatus and evacuated to 10-' Torr or less, and then In and Sn metal pieces were placed in a crucible at a weight ratio of 1:1, and the metal pieces were heated to 1 x 10-' by a resistance heating method.
Approximately 700 ml of ITO thin film was deposited in an oxygen atmosphere of about 7 Torr to form a transparent electrode 106. The substrate temperature at this time is 1
The temperature was 75°C. After cooling, the substrate was taken out, a permalloy mask was placed on the top surface of the transparent electrode 106, and the substrate was placed in a vacuum evaporation apparatus, and after being evacuated to below I x 10-' Torr, Ag was evaporated to a thickness of about 1.0 μm by resistance heating, and then combed. A tooth-shaped current collecting electrode 107 was formed for sample No.

It was set at 50.

The characteristics of this sample No. 50 were evaluated as follows.

AM-1,5 light (100 mw/cm') was irradiated from the transparent electrode 105 side of sample No. 50, and the open end voltage Voc,
The output when AM-1,5 light was irradiated through a 450 nm interference filter, and the change Δη in conversion efficiency before and after irradiation was measured by irradiating AM-1,5 light for 10 hours. The measurement results are shown in Table 35.

Separately, Si 02 ill formed by thermal oxidation on a Si single crystal wafer and a quartz glass substrate were prepared,
Z n S e l − as an n-type semiconductor layer was applied to each surface using a method and procedure similar to those described above.
X T e ll: H: A j2Ill s and n
Zn5l+-x Te1l as type semiconductor layer:
HID! and ZnSet-w T as a p-type semiconductor layer
e,: H: Li haze was formed individually. Regarding the obtained deposited film, the hydrogen atom content and the ratio of crystal grain regions in the film were measured according to the method described above. The measurement results are shown in Table 35.

Next, using the film forming apparatus shown in FIG.
2) with the structure shown in FIG. 1(A)
An n-junction photovoltaic device was fabricated. The lower electrode 1 was formed on the stainless steel substrate 101 in the same manner as in the method shown in Example 10.
The substrate cassette 30 has a Ag thin film deposited as 02.
2 and keeping the internal pressure of the film forming chamber 301 below 10-'Torr, the substrate 303 is heated to 300°C using an infrared heater 305.
C. and introduced raw material gas A and raw material gas B into the film forming chamber 301 through gas introduction pipes 308 and 309, respectively, under the conditions shown in Table 25. The internal pressure of the film forming chamber 301 is adjusted to l by adjusting the opening of the exhaust valve 314.

It was kept at OTorr. A high frequency power source 310 was connected to the cathode electrode 312 via a matching circuit 311, and 50 W of high frequency power of 13.56 MHz was immediately applied from the high frequency power source 310 to start film formation. After 2 minutes of discharge, n-type Zn5e:H:Aj+1li10
After forming the film No. 3, the high frequency power source was switched off and the introduction of gas was also stopped. After the internal pressure of the film forming chamber was evacuated to 10-' Torr or less, source gases A and B shown in Table 25 were introduced into the film forming chamber 301 again. While keeping the internal pressure at 1.0 Torr, 50 W of high frequency power was applied from the high frequency power supply 310.
After discharging for 0 minutes, the n-type Zn5a+-X TAX:
H: I-type Z n S e on AJl11!103
1-HT e 11 :H film 104 was formed. Thereafter, following the same procedure again and discharging for 2 minutes under the conditions shown in Table 25, an i-type Zn5e1-++Tem: Htll1
p-type Zn5e+-, Tem:H:Lll on 04
l [105 was formed.

Table 25 Conditions for manufacturing Zn5e1-, Te, :H (:M) film (Manufacturing method 17) After film formation, take out from the film formation chamber Example 1
Approximately 700 people deposited an ITO film as the transparent electrode 106 in the same manner as shown in Figure 2, and deposited an ITO film on top of it as the current collecting electrode 10.
A thin film was prepared, designated as sample No. 51, and its solar cell characteristics were evaluated.

The evaluation results are shown in Table 35.

Separately, 5totll! formed on the St wafer!
A quartz substrate was prepared, and each layer of Zn5e+- and Te was coated on each surface in the same manner as above.

:H:(:M) film was deposited. For each of the deposited films obtained, the hydrogen atom content and the ratio of crystal grain regions in the film were measured in the same manner as in Example 10. The measurement results are shown in Table 35.

11! Next, (3) of the present invention described above using the apparatus shown in FIG.
A pin-coupled photovoltaic device having the structure shown in FIG. 1(A) was manufactured using the manufacturing method described above.

A substrate on which an Ag lower electrode 102 is deposited on a stainless steel substrate 101 in the same manner as in the method and procedure shown in Example 1 is fixed to a substrate cassette 402 and transported into a film forming chamber 401. It was kept below 10-' Torr. On the cathode electrode 412, Zn5et-*Te, +
A polycrystalline target 416 was installed. The substrate 403 is maintained at 200° C. by an infrared heater 405, and the 26th
The raw material gases shown in the table were used and introduced into the film forming chamber 401 from the gas introduction pipe 408 under the conditions shown in the table.

The opening degree of the exhaust valve 414 was adjusted to maintain the internal pressure of the film forming chamber 401 at 0.05 Torr, and high frequency power of 300 W was applied to start film forming. After 3 minutes of discharge, n-type Z n S
@H-* T e * : 1(: A fL l
1l1103 was formed, the discharge was stopped, and the introduction of gas was also stopped.

Next, the chamber was evacuated to 10-' Torr or less, and the raw material gases shown in Table 26 were introduced under the conditions shown in the table.
The film was formed for 0 minutes, and the i-type Z n S @ 1-IIT a
II: Hll1104 was formed.

After that, the i-type Z n S @ l-1IT e w was discharged for 3 minutes using the same procedure again under the conditions shown in Table 26.
: P-type Zn5e+-++Te on the H film 104, :
H:Lill1105 was formed.

Table 26 Preparation conditions for Zn5e, -, Te, :H (:M) film (preparation method 18) After film formation, I was added to the sample as a transparent electrode 106.
TO film 700 and Ag@ were deposited as current collecting electrode 1-07, and characteristics as a solar cell were evaluated as sample No. 52. The evaluation results are shown in Table 35. Separately, Si
Prepare 5102M formed on a wafer and a quartz substrate, and coat each layer of Zn5e on each surface in the same manner as above.
, -1lTax:H(:M)M was deposited. For each of the deposited films obtained, the hydrogen atom content and the ratio of crystalline regions in the film were measured in the same manner as in Example 10. The measurement results are shown in Table 35.

In the method for manufacturing a photovoltaic device shown in Examples 10 to 12 of Table Jl, p-type, n-type, and n-type Zn5a+-m Te
1I:H(:M)Ill is manufactured by the same manufacturing method using the same film formation chamber, but the manufacturing methods for each of the p-type, n-type, and n-type semiconductor layers are different from each other. Also good.

An example of manufacturing a pin junction photovoltaic device in which the methods for manufacturing the p-type and n-type semiconductor layers and the method for manufacturing the l-type semiconductor layer are different will be described below.

First, a lower electrode 102 of Ag is placed on a stainless steel substrate 101.
The substrate on which 3,000 films were deposited is placed in the substrate cassette 30 in Figure 3.
n by the method and procedure shown in Example 11.
Type ZnS@I-m Te++ :H:AJlli1
03 was deposited. After the deposition, the film forming chamber was evacuated to 10-' Torr or less, and the substrate transfer device 306 was moved to the second film forming chamber 31B via the gate valve 307. here,
A deposited film forming apparatus shown in FIG. 2 is connected to the second film forming chamber 316 via a gate valve 307. Subsequently, in the same manner as shown in Example 10, l-type Z n S
e l -X T e H: H [il 04 as n-type Z n S e I -X T e x : A I
Continuously formed on t111I. Furthermore, the substrate transfer device 306 is returned to the first film forming chamber via the gate valve 307, and p-type Z is deposited using the method and procedure shown in Example 11.
n5e,-,TI! II:H:Li1li105 was deposited. The p-type Zn5e1− formed in this way
X T0n: H: L 1llllll, Example 1
With 1 Kuwa production similar to 0, 1TOfi! A transparent electrode 108 made of
Characteristics were evaluated as No. 3. The evaluation results are shown in Table 36.

Separately, 5iOzII! formed on a Si wafer!
and quartz substrates are prepared, and each layer is coated on each surface in the same manner as above. , ++:H(:
M) tli was deposited. For each of the deposited films obtained, the hydrogen atom content and the ratio of crystalline regions in the film were measured in the same manner as in Example 10. The measurement results are shown in Table 36.

Futane Group Engineering 1 ZnS:Al1 film was used as the n-type semiconductor layer, and ZnSel-XTam:H was used as the n-type semiconductor layer.
lii and Zn5l as the p-type semiconductor layer! 1-+
In this example, various pin junction type photovoltaic elements having the structure shown in FIG. 1 were manufactured using the +Te, :H:Li films respectively. , Method for producing a functional deposited film of the present invention (
A method similar to 1) to (3) was used, and the formation was performed under manufacturing conditions 19 to 21 shown in Table 27 below.

Table 27 N-type ZnS:Ajlli Preparation Conditions By the same operation as in Example 10, the above-mentioned No. 27
In manufacturing methods 19 to 21 of the table, n as an n-type semiconductor layer
Deposit a ZnS:Al film of the n-type ZnS:AJLI
The i-type Z n S e + -x T e w was formed on the il by the same operation as in Examples 10 to 12:
) till and p-type Zn5e:H:Li1li were stacked to form a semiconductor layer having a pin junction. In this way, a semiconductor layer having a pin junction shown in Table 37 was formed, and then a transparent electrode 106 and a current collecting electrode 107 were deposited in the same manner as in Example 10, and as samples Nos. 54 to 62, Characteristic evaluations similar to those in Example 10 as a photovoltaic device were performed. The evaluation results are shown in Table 37.

Separately, 5iO2tli formed on a Si wafer
and quartz substrates are prepared, and each layer of Zn5e:H:(:M)It! is coated on each surface in the same manner as above. was deposited.

For each of the deposited films obtained, the hydrogen atom content and the ratio of crystalline regions in the film were measured in the same manner as in Example 10. The measurement results are shown in Table 37.

E1ri±1 ZnO: All film is used as the n-type semiconductor layer, and i-type ZnS e + -* T e w is used as the l-type semiconductor layer.
r: 8111 and P- as the p-type semiconductor layer.
A Zn5el-x Te, l:H:Li film was formed to produce a pln junction type photovoltaic device having the structure shown in FIG. 1(A).

The n-type ZnO:All film was produced in the same manner as in Examples 10 to 12, except that the production conditions were as shown in Table 28 below.

Table 28: Fabrication conditions for n-type ZnO:All Under the fabrication conditions shown in Table 28, n-type ZnO:Af was deposited on an Ag electrode formed by vapor deposition on a stainless steel substrate.
tf'J is formed into a film, and then this n-type ZnO: All
On the Li film 3, an i-type Zn5a1-, Te, :H film and p
Type Z n S a , -1l T em : H:
A film of L t Ill was formed. After that, this p-type Zn5
el-x Te1I:H:ITO film and A on Li film
g Current collecting electrodes were sequentially laminated.

According to such a procedure, pin junction type photovoltaic elements (sample Nos. 63 to 71) were produced.

Table 38 shows the evaluation results obtained by measuring the characteristics of these samples.

Separately, 5tozll! was formed on a Si wafer.
and quartz substrates were prepared, and each qZnSe:H:(:M)III was deposited on each surface in the same manner as above. Example 1 for each deposited film obtained
The hydrogen atom content and the ratio of crystalline regions in the film were measured in the same manner as in Example 0. The measurement results are shown in Table 38.

Zn5eI-1lTell:
H:Aj! ZnS with Ill as the l-type semiconductor layer
e, -.

T e w : u Ill as a p-type semiconductor layer and Z
Various pin junction type photovoltaic elements having the structure shown in FIG. 1(A) were manufactured using nTe:Li films.

In this example, the method for forming p-type ZnTe:Li1 is the method for manufacturing a functional deposited film (1') of the present invention.
) to (3) were used, and the formation was performed under manufacturing conditions 25 to 27 shown in Table 29.

By the same operation as in Example 10, the above-mentioned 24th electrode was deposited on the stainless steel substrate on which the Ag electrode as the lower electrode was deposited.
n-type Zn5e+-x Te, :H:Aft as an n-type semiconductor layer under manufacturing conditions 16 to 18 in Tables 26 to 26
and i-type Zn5et-, Te, as an l-type semiconductor layer.
:H film is deposited and the i-type Zn5el+II Te,I
:HI]! p-type ZnT under the conditions shown in Table 29 above.
e: Li1li was stacked to form a semiconductor layer having a pin junction.

In this way, a semiconductor layer having a pin junction as shown in FIG.
, 72 to 80, Example 10 as a photovoltaic element
Characteristic evaluations similar to those were performed. The evaluation results are shown in Table 39.

Separately, a Si film and a quartz substrate formed on a Si wafer are prepared, and Z n S e r −++ T e *:H: of each layer is applied to each surface in the same manner as above.
(:M)III was deposited. For each of the deposited films obtained, the hydrogen atom content and the ratio of crystalline regions in the film were measured in the same manner as in Example 10.

The measurement results are shown in Table 39.

Table 29 P-type ZnTe: Li film production conditions dog! (
++11 n-type Zn5eI-, Te as the n-type semiconductor layer.

:H:Anll! and n-type Zn5 as the l-type semiconductor layer.
Fig. 1(A)
In this example, p-type Zn5e: Li1
As a method for forming li, a method according to the method (1) to (3) for manufacturing a functional deposited film of the present invention is used.
The formation was performed under manufacturing conditions 28 to 30 shown in the table.

In the same manner as in Example 10, an n-type Zn5e+ layer was formed as an n-type semiconductor layer on a stainless steel substrate on which an Ag electrode as a lower electrode was deposited under manufacturing conditions 16 to 18 shown in Tables 24 to 26. -*Tex:H:A1wA and n-type Zn5e+-++ as l-type semiconductor layer Te, l:
A H film was deposited, and p-type ZnTa+-, Te,: was deposited on the i-type Zn5a1-, Te, :H film under the conditions shown in Table 30.
H: Li films were stacked to form a semiconductor layer having a pin junction. In this way, a semiconductor layer having a pin junction as shown in Table 40 is formed, and then the main transparent electrode 106 is formed.
and current collecting electrode 107 were deposited in the same manner as in Example 10, and the characteristics of the photovoltaic elements were evaluated in the same manner as in Example 10 using samples Nd, 81 to 89. The evaluation results are shown in Table 40. Separately, a 5loz film formed on a Si wafer and a quartz substrate were prepared, and Zn S e I-X T e of each layer was applied to the surface of each in the same manner as above.
x'': H(: M) II was deposited. The hydrogen atom content and the ratio of crystalline regions in each of the resulting deposited films were measured in the same manner as in Example 10.

The measurement results are shown in Table 40.

Table 30: P-type Zn5e; H: Li1li production conditions Characteristic evaluations similar to those in Example 10 were performed. The manufacturing method will be described below.

500 people formed an ITO film as a transparent electrode on a 7059 glass substrate 101 manufactured by Corning Inc. by sputtering method, and performed P using the same operation and fabrication properties as in Example 10 using the substrate. Type Zn5et-, Tax: H
: Li1ll and i-type Zn5el-x T611
: Hlli was deposited. Subsequently, a -n type semiconductor layer 103 was deposited using the manufacturing method shown in Table 31 below.

Table 31 Next, an SOO film of Ag was deposited on the semiconductor layers formed up to the n-type semiconductor layer by electron beam evaporation to form the lower electrode 102. These samples were designated as sample no.

It was set at 90-92. The characteristics of each sample as a photovoltaic element were evaluated in the same manner as in Example 10, and the results of 0 or more were evaluated in the 41st test.
They are summarized in the table.

Separately, s iOx I formed on a Si wafer
II and a quartz substrate were prepared, and each layer of Zn5e1- and Te was coated on each surface in the same manner as above.

;H (:M) film was deposited. For each deposited film obtained, the hydrogen atom content and the ratio of crystalline regions in the film were measured in the same manner as in Example 10.
Shown in the table.

Separately, the 32nd film was placed on a stainless steel substrate on which ITO was deposited.
A p-type semiconductor Fltos was deposited using the manufacturing method shown in the table.

Subsequently, an i-type ZnSe, -xTell:H film and an n-type Zn5e+-1ITax:HAj2 film were deposited under the same operation and manufacturing conditions as in Example 10. Sample No. 93.94 was obtained in the same manner as Sample No. 92, and the characteristics were evaluated in the same manner.

The measurement results are shown in Table 41. vinegar.

Table 32: Zn5a+-x Te,:H film of i-type semiconductor layer: In order to see how the photovoltaic device characteristics change depending on the manufacturing conditions of the H film, The 4+'fl pin junction type photovoltaic device shown in FIG. A power device and an l-type Zn5a:H single layer film were prepared and evaluated in the same manner as in Example 10. The results are shown in Table 42 as samples No. 95-97.

Separately, prepare the 5i02 film and the quartz substrate formed on the St.
In the same manner as in cases 5 to 97, l-type Zn5a+ -If
Tex: )111% deposited. For each of the deposited films obtained, the hydrogen atom content and the ratio of crystalline regions in the film were measured in the same manner as in Example 10. Measurement results 'i! It is shown in Table A42.

Table 33 I-type Zn5a:l(:Li) was produced using the same production conditions and operating procedures as shown in Example 1O, except that the production conditions for Li were changed as shown in Table 34. A pin junction type photovoltaic element and an l-type Zn5a having the structure shown in
, Te1l: Htl! was prepared and evaluated in the same manner as in Example 10. The results are sample No. 98-1.
It is shown in Table 42 as 00.

Table 34: Ratio of raw material gas introduction conditions during film formation of l-type Zn5al-, Te process, same as Comparative Example 3.

:I-type Zn5a+-x Te
The 1l:H film was prepared using the structure shown in Fig. 1(C) of a-5l:H by the glow discharge method using the apparatus shown in Fig. 3 and the following procedure. A pin-type photovoltaic device was produced.

That is, first, approximately 1000 pieces of Ag were deposited on a stainless steel substrate 101 measuring 50 mm x 50 m+11 by sputtering to form an electrode 102 . After that, the substrate is connected to the electrode 1.
02 was fixed to the substrate cassette 302 facing downward, and the internal pressure of the film forming chamber 301 was evacuated to below to-' Torr.

The substrate temperature was maintained at 250° C. using a heater 305.

S i H4 gas, H2 gas,
PH3 gas (diluted with H2 to a concentration of 1%) at 30 SCCM, 40 SCCM, respectively.
The gas was introduced from the gas inlet 30B at a flow rate of 10 SCCM. The inside of the film forming chamber 301 was maintained at 0.05 Torr, and 50 W of high frequency power was applied and discharge was maintained for 3 minutes to form an n-type A-S.
t: Hilllo8 was deposited. After that, the high frequency power was stopped, the gas introduction was also stopped, and the inside of the film forming chamber 301 was heated to 10-'Tor.
S i H4 from each zero-order cylinder evacuated to below r
Gas, H2 gas 30 SCCM, 40 S respectively
CCM was introduced into the film forming chamber 301 at a flow rate of CCM, and discharged at 0.5 Torr and 70 W for 60 minutes in the same manner as described above to form an i-type A.
-3i: After forming the H film 109, the discharge and gas introduction are stopped and the inside of the film forming chamber 301 is evacuated to 10-' Torr or less, and SiH4 gas, H2 gas, 82
Ha gas (diluted to 1% concentration with H2 gas) at 30 SCCM, 200 Sll:CM, and 20
Introduced into the SCCM film forming chamber 301, the internal pressure was 0.6 Torr.
, p-type A-3t:H by discharging for 2 minutes with high frequency power SOW
A film of illllo was formed. After the film formation was completed, the sample was taken out, and an ITO electrode 106 and an Ag current collecting electrode 107 were formed in the same manner as in Example 1 to produce a pin junction type A-Si photovoltaic device. The photovoltaic properties of this sample were evaluated, and the results are shown in Table 42. Sample No.

101.

Table 35 Table 37 Table 38 Table 40 Table 39 Table 41 Table f542 Characteristic evaluation results of each sample Table 33 to Table 33 show the characteristics evaluation of each sample according to Examples 10 to 18 and Comparative Examples 3 to 5 Shown in Table 40.

The characteristics evaluation items as a photovoltaic element are AM-1,
Open end voltage (V) under 5 light (100 mw/cm') irradiation
oc), AM transmitted through a 450 nm interference filter
-1.5 Relative output value under irradiation (A produced in Comparative Example 2 of the output of each electromotive force element under interference filter transmitted light)
Relative value for the output of a 3t pin type photovoltaic element, )
, the rate of change in photoelectric conversion efficiency before and after continuous 10-hour irradiation with AM-1 light (Δη/η.: Δη is the amount of change in photoelectric conversion efficiency, η
. indicates the initial photoelectric conversion efficiency), and these evaluation results are shown.

In addition, the znse used to construct each photovoltaic element
Each Z n S film was prepared in order to confirm whether the l-++ Te, :H (:M) film was controlled to the hydrogen atom content and crystal grain area ratio in the film specified in the present invention.
e l-*T e A pin junction type photovoltaic element is a p-type Zn5el- in which the content of hydrogen atoms in the film and the ratio of crystal grain area per unit volume are limited to specific ranges on a stainless steel substrate.
1lTe, :H:Li film, i-type Z n S e l-w
Tex: H film and n-type Zn5eI-xTe
,:H: An Al1 film was produced, and its pin junction was well formed, so the open end voltage was high, and the output under irradiation with AM-1,5 light transmitted through a 450 nm interference filter was as high as that of the conventional A- It was found that it is larger than a Si pin-type photovoltaic element, and that the rate of change in photoelectric conversion efficiency before and after continuous 10-hour irradiation with AM-1,5 light is small, that is, there is little photodeterioration.

In Example 14, n-type ZnS:A was deposited on a stainless steel substrate.
Deposit ILIA% i-type Zn5a+-x Te,:H film and p-type Zn5et-++Te++:H:Li film,
I tried to make a pin junction between them and created a photovoltaic device, but
Photovoltaic devices having good characteristics according to Examples 10 to 13 were obtained.

In Example 15, n-type ZnO:A was deposited on a stainless steel substrate.
l1111% n-type Zn5e1-1lTe,: Hll
l and p-type Zn5el-++ Te++: H: L
A photovoltaic device was produced by depositing i1lil and attempting pin-to-pin junctions between them, and photovoltaic devices having good characteristics as in Examples 10 to 13 were obtained.

In Example 16, n-type Zn5et was deposited on a stainless steel substrate.
-, Te1l:H:Al1 film, n-type Zn5eI-, Te
A photovoltaic device was fabricated by depositing l1:Hg and p-type ZnTa:Li films and attempting pin junctions between them, but a photovoltaic device having good characteristics as in Examples 10 to 13 was not obtained. Ta.

In Example 17, n-type Zn5e,
, 1Tell: H:AILlli, n-type Zn5eI-
, Tax:H film and p-type Zn5e:Li1l were deposited, and a pin junction was attempted between them to produce a photovoltaic device, but a photovoltaic device with good characteristics as in Examples 10 to 13 was not obtained. It was done.

In Example 18, p-type Zn5et-,
Te1l: H: Lid and n-type Zn5al-, T
ex: Deposit Htli, then n-type ZnS,
e I-++ T e *: H: A ItIll
Alternatively, a pin junction photovoltaic device was fabricated by depositing an n-type ZnS:Ai film or an n-type ZnO:AILH. Furthermore, separately, p-type Z
n, Ta:Li1li or p-type Zn5e:H:Li1l
was deposited and then i-type ZnS@,-,Te++:Hll
A pin junction photovoltaic device was fabricated by depositing i- and n-type Zn5al-, Te,: H: AJ2 films.

These pin type photovoltaic elements are all of Example 10.
It had good characteristics similar to those of 1F to 1F.

Example! 8, p-type Zn5e1. ”
re, :H:Li1ll or p-type ZnTe:1(:L
i1li or p-type Zn5e:H:t, tuL then l-type Zn5a, -, Te,:Hlli, then n-type Zn
S e +-8Tell :H:AJ! Film, n-type Zn
A photovoltaic device was fabricated by depositing O:AJltli and trying to form a pin junction between them. A photovoltaic device having good characteristics similar to those of Examples 10 to 17 was obtained.

In Comparative Example 3, in the method for manufacturing a photovoltaic device carried out in Example 10, n-type Zn5al-, Te.

: Characteristic evaluations of photovoltaic elements obtained under conditions in which the amount of H2 gas introduced during Hg production was varied were compared. The hydrogen atom content and the ratio of crystal grain regions in the obtained n-type Zn5al-xTe, :H:Li film both deviated from the specified values, and as a result, the electrical properties also differed from those of the example. It was inferior to 10 to 18.

In Comparative Example 4, in the method for manufacturing a photovoltaic device carried out in Example 10, L-type ZnS@, -xTe++:Hlli
l-type Z- with different ratios of Se and Te obtained under conditions where the amounts of DESe gas and DETe gas introduced at the time of ll were changed.
A comparison of the characteristics of photovoltaic devices fabricated using nsel- and Te11 was conducted. The obtained l-type Z n S
a l -II T ex : The hydrogen atom content and the ratio of crystal grain regions in the H film both deviate from the specified values, and as a result, the electrical characteristics also differ from those in Example 10.
It was inferior to those of 1 to 18.

In Comparative Example 5, a conventional A-5i type pin type photovoltaic device was produced as a comparison target for evaluating the characteristics of the photovoltaic device of the present invention. However, the open circuit voltage was lower than that of any of the photovoltaic devices of the present invention, and the photodeterioration was also large.

[Brief explanation of the drawing]

FIGS. 1A and 1B are schematic diagrams of typical examples of the layer structure of the photovoltaic device of the present invention. FIG. 1(C) is a schematic diagram of the layer structure of a photovoltaic device produced in a comparative example. FIG. 2 is a schematic diagram of an example of a deposited film forming apparatus for implementing the method (1) of the present invention. FIG. 3 is a schematic diagram of an example of a deposited film forming apparatus for carrying out the method (2) of the present invention. FIG. 4 is a schematic diagram of an example of a deposited film forming apparatus for carrying out the method (3) of the present invention. FIG. 5 shows the results in experiments A (2) and (3) of the present invention.
FIG. 2 is an explanatory diagram of the relationship between the measurement results between the ratio of the crystal grain region of the sample and the hydrogen atom (H) content in the film. FIG. 6 is an explanatory diagram of the relationship between the hydrogen content in the film and the rate of change in the conductivity of the film in Experiment B of the present invention. FIG. 7 is an explanatory diagram of the relationship between the hydrogen content in the film and the drift/mobility of holes in Experiment B of the present invention. FIG. 8 is an explanatory diagram of the relationship between the hydrogen content in the film and the dark conductivity of the film in Experiment C of the present invention. FIG. 9 is an explanatory diagram of the relationship between the hydrogen atom content in the film and the ratio of crystal grain regions in the film in Experiment C of the present invention. FIG. 10 is an explanatory diagram of the relationship between the flow rate of hydrogen gas and dark conductivity during film formation in Experiment C of the present invention. FIG. 11 is an explanatory diagram of the relationship between the measurement results between the ratio of the crystal grain region of the sample and the hydrogen (H) content in the film in Experiments D (2) and (3) of the present invention. FIG. 12 is an explanatory diagram of the relationship between the hydrogen content in the film and the rate of change in the conductivity of the film in Experiment E of the present invention. FIG. 13 is an explanatory diagram of the relationship between the hydrogen content in the film and the drift mobility of holes in the experimental results of the present invention. FIG. 14 is an explanatory diagram of the relationship between the hydrogen content in the film and the dark conductivity of the film in Experiment F of the present invention. FIG. 15 is an explanatory diagram of the relationship between the hydrogen content in the film and the ratio of crystal grain regions in the film in Experiment F of the present invention. FIG. 16 is an explanatory diagram of the relationship between hydrogen content and dark conductivity in Experiment F of the present invention. FIG. 17 is an explanatory diagram of the relationship between the hydrogen atom content in the film and the photoconductivity of the film in Experiment G of the present invention. Figure 18 shows Se and Te in the film in Experiment G of the present invention.
FIG. 2 is an explanatory diagram of the relationship between the amount ratio of and photoconductivity. FIG. 19 is an explanatory diagram of the relationship between the hydrogen atom (H) content in the film and the dark conductivity when the amount ratio of 30% Te in the p-type doped film is used as a parameter in Experiment H of the present invention. It is. FIG. 20 is an explanatory diagram of the relationship between the amount ratio of Se and Te in the P-type doped film and the dark conductivity in Experiment H of the present invention. FIG. 21 is an explanatory diagram of the relationship between the amount ratio of 30% Te in the n-type doped film and the dark conductivity in Experiment (1) of the present invention. Figure 22 shows Se and Te in the film in Experiment J of the present invention.
FIG. 2 is an explanatory diagram of the relationship between the quantity ratio of and the optical band gap. Figure 23 shows Se and Te in the film in the experiment of the present invention.
FIG. 3 is an explanatory diagram of the relationship between the amount ratio of and the ratio of crystal grain regions in the film. Regarding FIG. 1, 100.111... Photovoltaic element, 101... Support, 102... Electrode, 103... N-type semiconductor layer, 1
04... I-type semiconductor layer, 105... P-type semiconductor layer, 106... Transparent electrode, 107... Current collecting electrode, 1
08 ・n-type A-S i semiconductor layer, 109 = i
Regarding the type A-5i semiconductor layer, 110...P type A-Si semiconductor layer, FIGS. 2, 3, and 4,

Claims (8)

[Claims] (1) A photovoltaic element that generates photovoltaic force by joining a p-type semiconductor layer, an i-type semiconductor layer, and an n-type semiconductor layer,
Among the semiconductor layers, at least an i-type semiconductor layer is composed of zinc atoms, selenium atoms, and at least hydrogen atoms,
The hydrogen atoms are contained in an amount of 1 to 4 atomic%,
1. A pin-type photovoltaic device comprising a deposited film in which the ratio of crystal grains per unit volume is 65 to 85% by volume. (2) The p-type semiconductor layer and/or the n-type semiconductor layer are composed of zinc atoms, selenium atoms, and at least hydrogen atoms,
A deposited film containing a type or n-type doping agent, containing the hydrogen atoms in an amount of 1 to 4 atomic%, and having a ratio of crystal grains per unit volume of 65 to 85% by volume. The pin-type photovoltaic device according to item (1). (3) The p-type doping agent is Group 1 or V of the periodic table.
The pin-type photovoltaic device according to claim 2, which is a group element. (4) The pin-type photovoltaic device according to claim (3), wherein the p-type doping agent is a lithium atom. (5) A photovoltaic element that generates photovoltaic force by joining a p-type semiconductor layer, an i-type semiconductor layer, and an n-type semiconductor layer,
Among the semiconductor layers, at least the i-type semiconductor layer is composed of zinc atoms, selenium atoms, tellurium atoms, and at least hydrogen atoms, and the atomic ratio of the selenium atoms to the tellurium atoms is 1:9 to 3. 7 and the hydrogen atom is 1
1. A pin-type photovoltaic device comprising a deposited film containing crystal grains in an amount of 65 to 85% by volume per unit volume. (6) The p-type semiconductor layer and/or the n-type semiconductor layer is composed of zinc atoms, selenium atoms, tellurium atoms, and at least hydrogen atoms, and contains a p-type or n-type doping agent, and the selenium atoms and tellurium atoms is in the range of 1:9 to 3:7 in terms of atomic ratio, and the hydrogen atoms are 1 to 4ato
6. The pin-type photovoltaic device according to claim 5, wherein the pin-type photovoltaic device is constituted by a deposited film containing mic% of crystal grains and a ratio of crystal grains per unit volume of 65 to 85% by volume. (7) The pin-type photovoltaic device according to (6), wherein the p-type doping agent is an element of Group I or Group V of the periodic table. (8) The pin-type photovoltaic device according to claim (7), wherein the p-type doping agent is a lithium atom.