KR840001163B1 - Photoelectric device - Google Patents

Abstract

A photoelectric device having at least a predetermined impurity region which is disposed in a semiconductor substrate, and a photoelectric converion portion which is constructed by stacking an electrode layer lying in contact with at least a part of the impurity region, a photoconductive material layer overlying the electrode layer, and a transparent electrode overlying the photoconductive material layer, characterized in that the photo conductive material layer is made of an amorphous chalcogenide material which princi- pally contains Se, is disclosed.

Description

Photoelectric conversion device

1 is a view showing the principle of a solid state imaging device,

2 is a cross-sectional view of the recall portion,

3 is a component distribution diagram of a representative photoelectric conversion material layer according to the present invention,

4 to 9 are each a cross-sectional view of a main portion showing the manufacturing process of the solid-state imaging device of the present invention,

10 is a plan view of the solid state imaging device of the embodiment;

12 is an explanatory diagram of an embodiment using a CCD as a scanning circuit,

13 is a sectional view of a CCD transmission region,

14 is a cross-sectional view of a light receiving portion.

The present invention relates to a photoelectric conversion device using a photoconductor layer. Conventionally, there is a solid state imaging device as a representative example of a photoelectric conversion device using a photoconductor layer.

The solid-state imaging device arranges a plurality of solid elements having a photoelectric conversion function and a signal accumulation function, forms an imaging surface by mapping each solid element to one time, and sequentially scans the imaging surface to convert external image information into an electrical signal. It is to let. In particular, the photoconductor layer forming the imaging surface is formed so as to cover the semiconductor substrate on which the switch, the scanning circuit, or the like is formed.

An example of such a solid state imaging device is clearly described in Japanese Patent Application Laid-Open No. 51-10715. The solid state imaging device has features such as small size, light weight, and no need for high voltage, but has not yet achieved practically usable characteristics.

There are some difficulties such as insufficient sensitivity, spectral sensitivity, and the like, and inherent problems of the solid state imaging device, such as the occurrence of white grooves on the reproduction screen.

A photoelectric cell having a predetermined impurity region formed in a semiconductor substrate and having an electrode layer in contact with at least a part of the impurity region, a photoconductive material layer on top of the photoconductive material layer, and a photoelectric conversion section formed by stacking a transmissive electrode on top of the photoconductive material layer. In the converter, the present invention is characterized in that the photoconductive material layer is composed of an amorphous chalcogenide material mainly composed of Se. Moreover, it is preferable to add and increase Te to a part of amorphous chalcogenide material layer mainly having this Se.

As the photoconductive material layer, the following four layers (a) to (d) may be divided into a structure in which adjacent layers are sequentially stacked.

(a). A first portion containing Se and having at least one of Te or Se to form a deep level, wherein the amount of Te and the amount of element to form a deep level in Se are on average 10 atomic percent or less, respectively.

(b). A second part containing Se and having a peak concentration of at least 15 atomic percent in a continuous distribution of elements which make a deep level in Se added thereto.

(c). A third part containing Se and having a peak concentration of at least 15 atomic% in the continuous distribution of Te added thereto.

(d). A fourth portion containing Se, and wherein at least one of the elements that make the deep level in Te or Se is added so that the amount of Te and the element that makes the deep level in Se are each on average 15 atom% or less.

In forming the photoconductive material layer as described above on a semiconductor substrate having a region on the surface, such as a solid state imaging device, during the formation of at least one photoconductor layer formed on the semiconductor substrate or the photoconductor After forming the layer, it is highly preferable to planarize the photoconductor layer by heat treatment at a temperature equal to or more than the softening point of the photoconductor.

In this process, discontinuities in the photoconductor layer due to the back surface of the substrate can be eliminated. Therefore, it is possible to prevent the occurrence of white grooves or the like on the reproduced image using the photoelectric conversion device. The invention is explained in more detail according to the drawings.

FIG. 1 is a diagram showing the principle of a solid state imaging device, in which each element 14 is arranged in a matrix and read out by the XY address method one by one. The selection of each cycle is made by the horizontal scan signal generator 10 and the vertical scan signal generator 12. 13 is a switch part connected to each element, and 15 is an output terminal.

The following is an example of a structure of the recovery part of such a solid-state imaging device. As shown in FIG. 2, the photoconductive film 8 serving as a photoelectric conversion is integrated on the IC substrate by integrating a scanning circuit and a switch circuit on the Si substrate 1. Referring to the principle of operation of Figure 2, the incident light 11 reaches the photoconductive film 8 through the transparent electrode (9). Here, light is absorbed to generate electron hole pairs, and their carriers are accumulated in the electrode 7 by the bias voltage V _T. The accumulated carriers are switched by an insulated gate field effect transistor (hereinafter, referred to as a MOSFET) formed of a source 2, a drain 3, and a gate 4 formed on the semiconductor substrate 1, and the signal line 5 It is taken out through). 6 is an insulating film. 12 of the back surface of the semiconductor substrate 1 is generally grounded as an electrode. In this structure, since the scanning circuit and the photoelectric conversion section are separated, not only the resolution and the photosensitivity are reduced, but also the light does not reach the Si substrate, so that blooming does not occur well.

As a material of the photoconductive film 8 for realizing such a structure, an amorphous chalcogenide material mainly composed of Se as described above is particularly preferable. In addition, the amorphous chalcogenide material layer has a structure as follows, whereby a solid-state imaging device having particularly good characteristics can be provided.

3 is a component distribution diagram showing the configuration of this photoconductor layer. Part of a of FIG. 3 is composed of Se layer containing at least one selected from the group of elements which make deep level among Te or Se, and the amount of elements which make deep level among Te or Se is below 10 atomic% each. However, the Se layer may be used only if the service life is not a problem.

The element considered to make a deep level in Se may be one of compounds containing at least one of Group IV elements such as Si, Ge, and other Group Vb elements such as As, Sb, and Bi. These elements may coexist with Te or may contain only these elements.

The element which makes such a deep level has a very small change in signal current, especially after the device is operated continuously for a long time, and the afterimage phenomenon is remarkably reduced.

The portion of a usually uses a film thickness of 0.5 to 10 µm, and mainly travels holes generated in the portion c, thereby reducing the capacity of the photoconductor and removing pinholes and the like. The film thickness of this a becomes like this. More preferably, it is 1-4 micrometers.

The part b of the iso diagram also introduces an additive that forms a deep level (As in this case) to enhance the effect of red sensitivity enhancement by Te contained in the part of the isograph C, and suppresses the signal current ageing when the device is operated for a long time. This is for part. In order to perform this action effectively, it is necessary that the concentration of the additive to make the deep level be a Se layer of 15 atomic% or more at the peak position of the continuous concentration distribution. And practically, 40 atomic% or less is used a lot. In addition, it is preferable that the shape of the concentration distribution of the additive forming the deep level in the portion of the same degree b is the highest at the interface in contact with the C portion, and smoothly decreases over 200 to 3000 kPa as it falls from the interface. This layer is generally used in thicknesses of 100 kPa to 5000 kPa.

In FIG. 3C, in order to obtain sufficient sensitivity in the visible light region, it is necessary that the peak concentration of the continuous distribution of the Te concentration should be Se layer having 15 atomic% or more, particularly preferably in the range of 15 to 30 atomic%. Moreover, it is preferable that the film thickness of this part should be 200-5000 kPa. Although the distribution of the Te concentration of the C portion in FIG. 3 is uniform and has a rectangular distribution, this shape is not limited to such a shape only.

It does not matter if you have a distribution that has a triangular, large, semicircular, or most complex shape. A part of d in FIG. 3 is a part necessary for making this film contact with the n-type transparent conductive film provided on the upper portion of the photoconductor layer to form rectified contact. In order to obtain stable rectifying contact, it is preferable that the Te concentration of this Se layer part does not exceed 15 atomic% on average.

Moreover, it is preferable that elements, such as As and Ge, added in order to increase thermal stability do not exceed 15 atomic% on average. The film thickness of this part needs to be 100Å or more. If the life is not a problem, only the Se layer may be used.

However, when it thickens more than necessary, since the amount of light which injects into the part of C decreases and a sensitivity will fall, 1000 mW or less is preferable practically.

In the case of the present invention, the concentration distribution of Te, As, Ge, etc. may be regarded as a macroscopically considered continuous distribution, and the concentration distribution may be controlled. In the case of the photoconductive film of the present invention, a thin layer of several tens to several tens of layers of these deposits is deposited on a deposition substrate using a rotary deposition apparatus using Se, As ₂ , Se ₃ , Te, Ge, or the like as an evaporation source. By superimposing thousands of layers cyclically, it is possible to obtain a macroscopic continuous distribution and to obtain a film having a desired component ratio or component distribution.

In this case, the component ratio of the continuous distribution is a continuous distribution of the average component ratios in the composite layer formed by the sum of each layer of one or two or more kinds of deposits that are cyclically deposited, that is, the composite layer formed by one cycle of rotary deposition. Is defined.

The chalcogenide amorphous material mainly composed of Se can be formed into a flat optical conductor layer by performing the above-described heat treatment, thereby obtaining a high quality reproduction image as described above. The solid-state image pickup device shown in cross section in FIG. 2 is first formed with a scanning circuit and a switch circuit on the Si substrate 1, and then an amorphous thin film is formed by, for example, a vacuum deposition method as a photoconductor layer. However, there are considerable examples on the Si substrate 1. The size of the step on the Si substrate is 1 to 2 mu m, but the photoconductive thin film formed thereon is generally 2 to 4 mu m. Therefore, discontinuities in the photoconductive film are generated in the stepped portions of the Si substrate. This discontinuity becomes a cause of a short circuit which acts as a pinhole when attaching the transparent electrode 9. This appears as white grooves in the image reproduced as a defect of the imaging device, degrading the image quality.

However, the chalcogenide amorphous material mainly composed of Se according to the present invention is a material which can compensate for this defect and obtain very good gray matter. That is, by depositing or depositing an amorphous thin film on a Si substrate on which a scanning circuit or the like is fabricated, the thin film is flattened by treatment at a temperature higher than the glass potential point of the amorphous thin film to remove the discontinuity of the thin film and thus appears on a television monitor. It is to remove the defect of the white groove. As said heat processing temperature, 50 degreeC or more is preferable. The heat treatment is more preferably at least 100 ° C or below the temperature at which the thin film material does not deteriorate. In practice, an amorphous material containing Se as an essential component is preferably 120 ° C. or lower. The atmosphere at the time of heating may be nitrogen, a rare gas, or in air.

When depositing while heating, about 15 minutes or less is preferable. In the case of heating after deposition, the heating time is about 5 minutes because the planarization of the layer becomes more than the softening point of the amorphous material. In addition, heating in a short time is also important in the sense of preventing the diffusion of added impurities. In addition, this method is not only limited to the solid state imaging device, it goes without saying that it can be applied when the photoconductor layer is provided on the substrate having the fin.

The present invention will be described in more detail with reference to the following examples.

Example 1

4 to 9 are cross-sectional views of the recovery section showing the manufacturing method of the solid state imaging device. The switch circuit formed on the semiconductor substrate, the scanning circuit portion, and the like are manufactured using a process of a conventional semiconductor device.

A thin SiO ₂ film of about 800 mW is formed on the P-type silicon substrate 20, and a Si ₃ N ₄ film of about 1400 mW is formed at a predetermined position on the SiO ₂ film. SiO ₂ film conventional CVD method, Si ₂ N ₄ film Si ₃ N _4, made of a CVD method spilled NH _4, N _2. The P diffusion region 21 is formed on the silicon substrate by the ion implantation method.

This diffusion region 21 is provided for better separation of the elements. Subsequently, silicon is locally oxidized in an H ₂ : O ₂ = 1: 8 atmosphere to form an SiO ₂ layer 22 (FIG. 4). This method is a local oxidation method of silicon for device isolation, commonly referred to as LOCOS. The above-described Si ₃ N ₄ film and SiO ₂ film are removed to form a gate insulating film of the MOS transistor as a SiO ₂ film. Subsequently, the gate portion 25 and the diffusion regions 26 and 27 made of polysilicon are formed, and again the SiO ₂ film 28 is formed thereon. In this film, the electrode outlets of the source 26 and the drain 27 are opened by etching (FIG. 5). As the drain electrode 29, 8000 Al of Al was deposited. Then, the SiO ₂ film 30 was formed to be 7500 mW, and then Al was deposited to 1 μm as the source electrode 31. 6 is a cross-sectional view showing this state.

A circuit such as a shift register is arranged around the light receiving area. In this way, the scanning circuit section is completed. A light receiving portion is formed on the scanning circuit portion. 10 shows a plan view of the Si substrate portion. 37 is a contact hole for an electrode. In the drawings, the same reference numerals indicate the same parts. A Se-As layer 32 containing 5 atomic% arsenic is formed on the semiconductor substrate thus prepared in a thickness of 3 mu m. 3 is a part of a of the component distribution diagram. As shown in FIG. 6, after forming a scanning circuit or the like on the semiconductor substrate 20, the back surface of the semiconductor substrate is generated. Therefore, in this state, as shown in FIG. 7, the surface of this Se-As layer is not flat because it antireflects the gap of the IC substrate. Next, the substrate was subjected to a heat treatment at 110 ° C. for 5 minutes in a nitrogen gas atmosphere.

Since the softening point of Se-As is about 70 ° C., the layer is softened by this heat treatment and flattened as shown in FIG. And as said heat processing temperature, 50 degreeC or more is preferable. More preferably, it is 80 degrees C or more and below the temperature which a thin film material does not deteriorate. In practice, an amorphous material containing Se as an essential element is preferably 120 ° C. or lower. The atmosphere at the time of heating may be nitrogen, ash gas, or air. A chalcogenide amorphous material mainly composed of Si does not occur in the photoconductive properties even with heat treatment.

And as a heating method, it is preferable to follow irradiation with a lamp (for example, halogen lamp) etc., for example. On this first layer 32, a second layer 33 (part of b) made of Se and As is deposited. In the case of depositing the second layer 33, Se, As ₂ and Se ₃ are put in separate deposition boats and evaporated at the same time. At this time, the concentration of As is first 5 atomic% by controlling the current flowing in the deposition boat of the As ₂ Se ₂ layer, and increases smoothly as the deposition proceeds, so that the end of the third layer 34 having a thickness of 500 to 1500 Å is obtained. To 15 atomic percent to 25 atomic percent. Subsequently, Se and Te are deposited at the same time on separate deposition boats to form the third layer 34 (part of C). Te is contained in the 3rd layer 34 similarly, the film thickness of the 3rd layer 34 is 500-2000 GPa, and Te concentration is 15 atomic%-25 atomic%. The Se containing 10 atomic% As as a fourth layer 35 (part of d) is deposited thereon at a thickness of 100 kPa to 500 kPa. The above deposition is carried out in a vacuum of 3 x 10 ^-6 Torr.

It is preferable to insert a blocking film 36 such as a CeO ₂ film on top of the fourth layer 35. Although this layer is not necessarily required, it is possible to suppress the dark current which causes the effect of disturbing the flow of holes. The material of this layer is Ce, Zn, Cd, B, Al, SD, Y, Si, Ge, Bi, Zr, Hf, Th, La, Sb, Bi, V, Nb, Ta, Fe, U, W, Mo The substance which has an oxide of at least 1 element selected from the group which consists of these etc. as a main component is preferable. Representative examples include CeO ₂ , CdO, B ₂ O ₂ , SC ₂ O ₃ , ZrO ₂ , ThO ₂ , Fe ₂ O ₃ , CoO, Co ₂ O ₃ , Pr ₂ O ₃ , Tc ₂ O ₃ , ReO ₃ , MgO , WO ₃ , PbCrO ₄ , Nb ₂ O ₃ , Ta ₂ O ₃ , Bi ₂ O ₃ , V ₂ O ₅ , Y ₂ O ₃ , HfO ₂ , La ₂ O ₃ , GeO ₂ , NiO, Cu ₂ O, MnO , U ₃ O ₈ , BeO, WO ₃ , Mo ₂ O ₅ , Al ₂ CoO _4, and the like. The blocking layer is usually installed at a thickness of about 100 kPa to 400 kPa.

The blocking layer is not limited to this example but can be widely used for the photoconductive layer according to the present invention. Subsequently, the transparent electrode 37 is formed to produce an amorphous film element. As the transparent electrode, an ultra-thin film such as gold or a transparent conductive film containing indium oxide and tin oxide that can be formed at low temperature may be used. In addition, a metal film or the like of the world may be used as the light transmitting electrode.

Finally, the conductor film 38 of the ohmic contact is provided on the other surface of the semiconductor substrate 20. In general, the conductor film 38 is grounded through the terminal.

Cr-Au was deposited on a portion of the transparent electrode using a mask, and wire bonded thereto to form a bias electrode. A high quality solid state imaging device with a high SN ratio and no blooming is obtained. The signal current with respect to the unit surface roughness of this apparatus was about 71nA / lx for the color temperature 3200 ° K white light source, and the spectral sensitivity was blue (450 nm) and 0.28 mA / kV (quantum efficiency 0.78).

Here, the effect of planarization by heating of the photoconductor layer is mentioned. The first table shows the result of comparing the above-mentioned case where the Se-As layer (first layer) was planarized with the case where the planarization was not performed.

[Table 1]

As can be seen from the first table, when the present invention is not used, the generation of very white grooves increases. In the present embodiment, an example in which the MOS field effect transistor is shown as the scanning circuit is not limited to this, but needless to say, for example, a CCO transmission region may be used as the scanning circuit. . It goes without saying that other circuit methods can also be used using MOS transistors.

In addition, although the following solid state imaging device is manufactured, there is no occurrence of white grooves in the reproduced image seen in the conventional apparatus as in the example described so far.

As in the above-described example, a switch circuit, a scan circuit portion, and the like are formed on a semiconductor substrate. 6 is a basic sectional view showing this state. Subsequently, a Se-As layer 32 containing 8 atomic% arsenic is formed to a thickness of 1 탆. The semiconductor substrate thus prepared is subjected to heat treatment for 3 minutes at 150 ° C in air.

Then, Se-As-Te layer (As: 2 atomic%, Te: 21 atomic%) (33) and Se-As layer (As: 6 atomic%) 34 were deposited by vacuum deposition, and then the transparent electrode 37 ). Finally, the conductor film of resistance contact is provided on the other surface of the semiconductor substrate 20. In general, the conductor film 38 is grounded through the terminal. 11 is a cross-sectional view showing this state.

This example is an example of a photoconductive film composed of three layers of Se-As layer, Se-As-Te layer, and Se-As layer. Needless to say.

Example 2

As in the first embodiment, a switch circuit, a scanning circuit, and the like are formed on a predetermined semiconductor substrate. Subsequently, the Se-Ge layer (germanium content 5 atomic%) is kept at a gas temperature of 60 ° C. and vacuum-deposited. Heat treatment at 100 DEG C for 3 minutes is carried out in the deposition apparatus. This process flattens the photoconductive film surface.

Se and Ge are respectively deposited on this layer by separate deposition boats at a vacuum degree of 3 × 6 ⁻⁶ Torr. At this time, the Ge concentration is 5 atomic% at the initial deposition, and smoothly increases as the deposition proceeds, so that the Ge concentration is 20-25 atomic% at the thickness of 500 to 100 의. Se and Te are then deposited to form C region of the photoconductive film. At this time, the Te concentration is 20 to 25 atomic% in the initial deposition phase, and then gradually decreases, and composition control is performed so as to be 0 to 5 atomic% at a film thickness of 1000 kPa. A 300 nm film of Se containing 10 atomic% Ge is formed in the d region of the photoconductive film.

As in Example 1, an amorphous thin film device is fabricated by forming a transparent electrode on the photoconductive film. In addition, even if Sb, Bi, or Si is used instead of Ge as an element for making a deep level in Se, a predetermined effect can be obtained. In addition, these elements may coexist, including As. Te may be used instead of the element which makes the deep level in Se, and Te and these elements may coexist.

Example 3

As in the first embodiment, a switch circuit, a scan circuit, and the like are formed on a predetermined semiconductor substrate. 6 is a cross-sectional view of the substrate showing this state. Next, Se-As layer (arsenic content of 8 atomic% or less) (32), Se-As, -Te layer (As: 2 atomic%, Te: 21 atomic%) (33), Se-As layer (As: 6 atomic %) 34 was maintained at a gas temperature of 60 ° C. and subsequently vacuum deposited. Subsequently, heat treatment at 100 ° C. for 3 minutes is applied in the deposition apparatus. This process flattens the photoconductive film surface. Subsequently, a transparent conductive film was formed to manufacture a solid state imaging device. Also in this example, the defect of the white flaw seen with the conventional apparatus does not occur.

Example 4

An example in which the CCD transfer area is used as the scanning circuit is shown. 12 shows a plan explanatory view of the arrangement of the elements. 50 is a horizontal clock terminal, 51 is a vertical clock terminal, 52 is an output horizontal transfer register, 53 is a vertical transfer gate, 54 is a vertical analog transfer register, 55 is a part of a chamber in which a diffusion region and a MOS type switch having the same source are combined. to be.

FIG. 13 is a sectional view of the CCD transfer area, and FIG. 14 is a sectional view of the recovery portion. In FIG. 13, electrodes 62 and 63 are formed on an Si substrate 61 via an insulating layer, and clock voltages of two phases are applied through 64 and 65. In FIG. As a result, potential wells in the Si substrate are moved to transfer charges. FIG. 14 is a cross-sectional view of a light receiving area, that is, a part of the element, 41 is a diffusion layer, 42 is an insulating layer, 43 is a metal electrode, 44 is a gate, 45 is a photoconductive film, and 46 is a transparent electrode. The CCD transfer region shown in FIG. 13 is continuously formed in this light receiving region. The transparent electrode 46, the photoconductive film 45, the metal electrode 43, and the like form a light receiving portion, and the switch region for moving the carriers to the transfer region where the organic carriers are formed has a substantial MOS switch at the portion having the gate 44. Forming.

An Si substrate having a CCD transfer region and a MOS switch portion is prepared and deposited on a vacuum deposition apparatus. Se-As layer (As: 8 atomic% or less) (3 micrometers in thickness) 45 is formed. In this state, the surface of the Se-Ae layer 45 is not flat to reflect the roughness of the gas. Next, the substrate was subjected to heat treatment at 110 ° C. for 5 minutes in a nitrogen gas atmosphere. And Se-As-Te layer (As: 2 atomic%, Te: 21 atomic%) (thickness 0.05㎛) Se-Ae layer (As: 6 atomic%) on the planarized Se-As layer 45 (thickness) 0.02 μm) 47 was subsequently deposited. The transparent electrode 48 is formed on this photoconductor layer as described above. Cr-Au was mask-deposited on a part of the transparent electrode and wire-bonded here to make a bias electrode. Finally, the conductor film 49 of the ohmic contact is provided on the other surface of the semiconductor substrate 20. In general, the conductor film 49 is grounded through the terminal.

The operation is briefly described using FIG. When light hits the light-receiving portion via the transparent electrode, the carrier induced by the optical signal is applied to the gate electrode between the diffusion region in the light-receiving portion 55 and the vertical analog transfer register 54 by applying a voltage to the vertical transfer register. It is moved to 54. The vertical transfer registers are sent to the output horizontal transfer registers 52 through the vertical transfer gate 53 one by one in the CCD driven through the two-phase vertical clock terminal 51. This horizontal transfer register is also a CCD driven through the two-phase horizontal clock terminal 50, and the charge corresponding to the signal is sent to the output and taken out as a signal output. The frequency of the two-phase drive may be selected so that the transfer of the horizontal transfer register is completed within the voltage pulse period applied to the vertical transfer gate.

Example 5

As in the first embodiment, a switch circuit, a scan circuit, and the like are formed on a predetermined semiconductor substrate. Subsequently, a Se-As layer (5 atomic% of arsenic content) was formed as in the above embodiment, but as a forming method, a 0.3 μm Se-As layer was deposited without heating first, and then the substrate was heated to 75 ° C. to give 3 μm Se-As layers as stated were deposited. In this process, the photoconductive film is planarized. Subsequently, substrate heating was stopped to deposit a Se-As-Te layer (As: 2 atomic%, Te: 21 atomic%) and a Se-As layer (As: 6 atomic%). After the deposition was completed, a transparent electrode was formed to obtain a good imaging device as in the above example. In the same manner, vapor deposition is performed without heating the 0.2 µm Se-As layer and heating deposition (80 ° C.) followed by heating 0.5 µm. Subsequently, the device which laminated | stacked Se-As-Te layer and Se-As layer was also manufactured as mentioned above. In this case, the same effect was obtained. Thus, forming a thin Se-As layer without heating first on the semiconductor substrate is useful for further lowering the probability of occurrence of scratches in the photoconductive film.

Claims (1)

A photoelectric conversion device having at least a first electrode in contact with a part of an impurity layer formed on a semiconductor substrate, a photoconductor layer formed on an upper portion of the first electrode, and a transmissive second electrode formed on an optical conductor layer. The first part (a part, in which the entire layer contains Se and at least one of the elements that make the deep level in Te or Se is added so that the amount of Te or the element which makes the deep level in Se is on average 10 atomic% or less, respectively) ), And a second portion (b portion) having a peak concentration of 15 atomic% or more in a continuous distribution of elements containing Se and added in it to create a deep level in Se, and a continuous portion of Te containing Se A third portion (C portion) having a peak concentration of 15 atomic% or more and at least one element containing Se and forming a deep level in Te or Se is added to form a deep level in the amount of Te or Se. Cattle sheep is at least formed by an average of 15 at% or less fourth portion (d area) each photoelectric conversion device, it characterized in that the parts are made in adjacent sequence.

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