JP5709730B2 - Thin film manufacturing method - Google Patents

Description

  The present invention relates to a method of manufacturing a thin film of a compound semiconductor.

There is a photoelectric conversion device including a light absorption layer made of an I-III-VI group compound semiconductor. As this I-III-VI group compound semiconductor, a chalcopyrite compound semiconductor such as Cu (In, Ga) Se ₂ (also referred to as CIGS) is employed.

  In this photoelectric conversion device, for example, a lower electrode layer made of, for example, Mo is formed on a glass substrate, and a light absorption layer made of an I-III-VI group compound semiconductor is formed on the lower electrode layer. ing. Further, a buffer layer made of ZnS or CdS or the like and a transparent upper electrode layer made of ZnO or the like are laminated on the light absorption layer in this order.

  By the way, various methods for forming a light absorption layer made of a group I-III-VI compound semiconductor have been proposed.

  For example, a film obtained by applying a fine powder of a group I-B element alone, a fine powder of a group VI-B element simple substance, and an organic metal salt containing a group III-B element in a solvent on a conductive substrate. A method has been proposed in which a thin film of a group I-III-VI compound semiconductor is formed by heat treatment (Patent Document 1, etc.). This heat treatment is performed in an inert gas or in a reducing atmosphere. Further, in Patent Document 1, when a VI-B element or a VI-B group element compound exists in an atmosphere in which heat treatment is performed, an alloy film and a VI-B group composed of an IB group element and a III-B group element are disclosed. It is described that the element and the element combine rapidly.

In addition, an organic metal salt solution containing an organic metal salt of a group I-B element and an organic metal salt of a group III-B element is deposited on a conductive substrate to form a film, and then the group VI-B element is added. A method of performing heat treatment in a non-oxidizing atmosphere is proposed (Patent Document 2, etc.). According to this method, a compound semiconductor thin film having a chalcopyrite structure based on IB-IIIB-VIB ₂ is produced.

  In addition, for example, a single source precursor in which Cu, Se, In, or Ga is present in one organic compound is used as a raw material for the I-III-VI group compound semiconductor. It has been proposed (Patent Document 3 etc.).

JP 2001-53314 A JP 2001-274176 A US Pat. No. 6,992,202

  In the film containing the raw material of the I-III-VI group compound, the organic component is thermally decomposed by heat treatment, and then the raw material elements react to form a polycrystal (semiconductor layer) of the I-III-VI group compound. .

  However, each constituent element of the I-III-VI group compound may disappear during the heat treatment, or the reaction may not be sufficiently performed in the entire film. For this reason, when a thin compound semiconductor layer having a large upper surface area is formed, the composition of the compound semiconductor layer is likely to vary.

  And the improvement in the photoelectric conversion efficiency in a photoelectric conversion apparatus may be prevented by the dispersion | variation in the composition in a compound semiconductor layer. Such a problem is common to thin film of compound semiconductor containing a chalcogen element.

  Therefore, a thin film manufacturing method that improves photoelectric conversion efficiency in a photoelectric conversion device using a compound semiconductor containing a chalcogen element is desired.

  The thin film manufacturing method which concerns on one aspect is a thin film manufacturing method which manufactures the thin film of the compound semiconductor containing a chalcogen element, Comprising: It has process (a)-(d). In the thin film manufacturing method, in the step (a), one or more substrates on which a first film containing at least a metal element other than the chalcogen element contained in the compound semiconductor is disposed are prepared. In the step (b), the one or more substrates are oxidized by heating the one or more substrates in an atmosphere containing at least one of moisture and oxygen, thereby causing the one or more substrates to be oxidized. A second film containing the metal element partially oxidized is formed on one main surface. In the step (c), the one or more substrates on which the second film is arranged on one main surface are arranged in a substrate arrangement region in one heating furnace. In the step (d), at least one of supply of the gas containing the chalcogen element into the one heating furnace by a plurality of gas supply units, and exhaust from the inside of the one heating furnace by a plurality of gas discharge units By adjusting one, the supply amount of the chalcogen element per unit time in each space region of a predetermined size in contact with each of the second coatings according to the distribution of oxygen content for each of the second coatings The compound semiconductor thin film is formed on the one or more substrates by heating the one or more substrates while flowing a gas containing the chalcogen element in a different manner.

  The thin film manufacturing method which concerns on another one aspect is a thin film manufacturing method which manufactures the thin film of the compound semiconductor containing a chalcogen element, Comprising: It has process (A)-(D). In the thin film manufacturing method, in the step (A), two or more substrates on which a first film containing at least a metal element other than the chalcogen element contained in the compound semiconductor is disposed are prepared. In the step (B), the two or more substrates are heated by heating the two or more substrates in an atmosphere containing at least one of moisture and oxygen, whereby the two or more substrates are oxidized. A second film containing the metal element partially oxidized is formed on one main surface. In the step (C), the two or more substrates on which the second film is arranged on one main surface are arranged in a substrate arrangement region in one heating furnace. In the step (D), at least one of supply of the gas containing the chalcogen element into the one heating furnace by a plurality of gas supply units, and exhaust from the inside of the one heating furnace by a plurality of gas discharge units By adjusting one, the supply amount of the chalcogen element per unit time differs in a space region of a predetermined size in contact with each second coating according to the oxygen content of each second coating. The compound semiconductor thin film is formed on the two or more substrates by heating the two or more substrates while flowing a gas containing the chalcogen element.

  According to any of the thin film manufacturing methods according to the above embodiment and the other embodiment, the photoelectric conversion efficiency in the photoelectric conversion device using the compound semiconductor containing the chalcogen element can be improved.

It is the schematic which shows the thin film manufacturing apparatus which concerns on one Embodiment. It is a figure which shows the XY cross section in the position shown with the dashed-dotted line II-II in FIG. It is a figure which shows the XY cross section in the position shown with the dashed-two dotted line III-III in FIG. It is a flowchart which shows the manufacturing flow of a photoelectric conversion apparatus. It is a figure which shows typically the state in the middle of manufacture of a photoelectric conversion apparatus. It is a figure which shows typically the state in the middle of manufacture of a photoelectric conversion apparatus. It is a figure which shows typically the state in the middle of manufacture of a photoelectric conversion apparatus. It is a figure which shows typically the state in the middle of manufacture of a photoelectric conversion apparatus. It is a figure which shows typically the state in the middle of manufacture of a photoelectric conversion apparatus. It is a figure which shows typically the state in the middle of manufacture of a photoelectric conversion apparatus. It is a figure which shows typically the state in the middle of manufacture of a photoelectric conversion apparatus. It is a figure which shows typically the state in the middle of manufacture of a photoelectric conversion apparatus. It is a top view which shows the structure of a photoelectric conversion apparatus typically. It is a figure which shows the XY cross section in the position shown with the dashed-dotted line XIV-XIV in FIG. It is a flowchart which illustrates the manufacturing flow of the photoelectric conversion apparatus containing the measurement of in-plane distribution of oxygen content. It is the schematic which shows the thin film manufacturing apparatus which concerns on a 1st modification. It is the schematic which shows the thin film manufacturing apparatus which concerns on a 2nd modification. It is the schematic which shows the thin film manufacturing apparatus which concerns on a 3rd modification. It is a figure which shows XY cross section in the position shown with the dashed-dotted line XIX-XIX in FIG. It is a figure which shows XY cross section in the position shown with the dashed-two dotted line XX-XX in FIG. It is a figure which shows the division of the area | region in the dry film which concerns on an Example. It is a figure which shows in-plane distribution of the oxygen concentration in the dry film | membrane which concerns on an Example. It is a figure which shows a mode that the heat processing are performed to the to-be-heated substrate which concerns on an Example. It is a figure which shows the in-plane distribution of the photoelectric conversion efficiency in the photoelectric conversion apparatus which concerns on an Example. It is a figure which shows in-plane distribution of the photoelectric conversion efficiency in the photoelectric conversion apparatus which concerns on the reference example 1. FIG. It is a figure which shows the in-plane distribution of the photoelectric conversion efficiency in the photoelectric conversion apparatus which concerns on the reference example 2. FIG.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the drawings, parts having the same configuration and function are denoted by the same reference numerals, and redundant description is omitted in the following description. Further, the drawings are schematically shown, and the sizes, positional relationships, and the like of various structures in the drawings are not accurately illustrated.

  1 to 3, FIG. 5 to FIG. 14 and FIG. 16 to FIG. 26, in order to clearly show the positional relationship between the heating furnace 2, each part attached to the heating furnace 2, and the heated substrates 5 and 5A, A right-handed XYZ coordinate system with the longitudinal direction of the heating furnace 2 as the X-axis direction is attached. Here, the longitudinal direction is a left-right direction as viewed in FIG. However, the arrangement relationship with respect to the heating furnace 2 is not drawn for the plurality of gas supply sources S6, the plurality of gas discharge adjustment units E7, and the control unit C1. Moreover, in FIG.1, FIG.16-18, and FIG. 23, a mode that gas flows is typically drawn with the arrow of the broken line.

<(1) One Embodiment>
<(1-1) Thin film manufacturing apparatus>
The thin film manufacturing apparatus 1 includes a heating furnace 2, a plurality of gas supply units 6, a plurality of gas discharge units 7, a heater 8, a plurality of gas supply sources S6, a plurality of gas discharge adjustment units E7, and a control unit C1. In FIG. 1, the XZ cross section for the heating furnace 2, the plurality of gas supply units 6, the plurality of gas discharge units 7, and the heater 8, the plurality of gas supply sources S 6, the plurality of gas discharge adjustment units E 7, and the control unit C 1. Are shown schematically. In FIG. 2, the XY cross section of the heating furnace 2 and the heater 8, the several gas discharge part 7, and the several gas discharge adjustment part E7 are shown typically. In FIG. 3, the XY cross section of the heating furnace 2 and the heater 8, the several gas supply part 6, and several gas supply source S6 are shown typically.

  The heating furnace 2 is a housing having a substantially rectangular parallelepiped box shape. The outer edge of the heating furnace 2 has two surfaces substantially parallel to the XY plane, two surfaces substantially parallel to the XZ plane, and two surfaces substantially parallel to the YZ plane. The heating furnace 2 has an internal space 2I. The heating furnace 2 is not limited to a substantially rectangular parallelepiped, and may have an internal space in which a heating object can be placed. Moreover, as a material of the heating furnace 2, for example, a nickel-base superalloy having excellent heat resistance can be employed. The nickel-base superalloy is an alloy containing nickel in an amount of 50% by mass or more. Examples of nickel-based superalloys include Inconel (registered trademark).

  A cassette 4 is arranged in the internal space 2I. Two or more predetermined numbers of substrates (also referred to as heated substrates) 5 are mounted on the cassette 4 in a state of being arranged in one direction. Here, one direction is the Y direction, and the predetermined number of 2 or more is 7. Further, in the cassette 4, the main surfaces of the front and back surfaces of each heated substrate 5 are substantially parallel to the XY plane. That is, the adjacent substrates 5 to be heated face each other. Moreover, the space | interval of the to-be-heated board | substrate 5 with which the cassette 4 is mounted | worn should just be made substantially constant, for example.

In FIG. 1 to FIG. 3, reference numeral 51 is assigned to the substrate to be heated 5 arranged _first from the −Y side, and m is arranged from the −Y side (here, m is an integer of 1 to 7). Reference numeral 5 _m is given to the substrate 5 to be heated. The cassette 4 mainly includes twelve frames connected to each other surrounding a substantially rectangular space area (also referred to as a substrate arrangement area) 4R in which two or more heated substrates 5 are arranged. 1 to 3, the outer edge of the cassette 4 is indicated by a one-dot chain line.

The plurality of gas supply units 6 are arranged in the other direction perpendicular to one direction in the lower part of the internal space 2I. Here, the other direction is the X direction. Moreover, what is necessary is just to make the space | interval of the adjacent gas supply parts 6 substantially constant, for example. In FIG. 1 and FIG. 3, reference numeral 61 is assigned to the gas supply unit 6 arranged _first from the −X side, and nth (here, n is an integer of 1 to 8) from the −X side. Reference numeral 6 _n is attached to the gas supply section 6 arranged.

The gas supply unit ₆₁ through ₈ is a tubular member that extends along the upper portion of the inner space 2I from the end of the -Y side in the + Y direction. In addition, each gas supply unit ₆₁ through _8, a plurality of openings 60 are provided on the + Z side. In each of the gas supply units 6 _{1 to} 6 ₈ , a plurality of openings 60 are arranged at substantially constant intervals in the Y direction.

The plurality of gas supply sources S6 supply a predetermined gas to the plurality of gas supply units 6. Each gas supply source S6 has, for example, a tank, a pump, a pipe, a valve, and the like that store a predetermined gas. In FIG. 1 and FIG. 3, the gas supply source S6 arranged _first from the −X side is denoted by S61, and is nth (here, n is an integer of 1 to 8) from the −X side. The gas supply source S6 that is arranged is labeled S6 _n .

Then, n-th gas source S6 _n, are connected to the n-th gas supply section 6 _n, adjusts the supply amount of the predetermined gas to the interior space 2I by n-th gas supply unit 6 _n. Thereby, each gas supply part 6 supplies predetermined gas toward the board | substrate arrangement | positioning area | region 4R. The predetermined gas is a gas containing a chalcogen element. The chalcogen element may be at least one of Se, Te, and S. Furthermore, the predetermined gas may include at least one gas (also referred to as non-oxidizing gas) of a reducing gas and an inert gas in addition to the gas containing the chalcogen element.

  Here, the supply of the chalcogen element contained in the gas flowing per unit time in each space region of a predetermined size in the substrate arrangement region 4R by the supply amount of the predetermined gas to the internal space 2I by each gas supply unit 6 The amount can be adjusted.

  In this case, for example, each gas supply source S6 adjusts the supply amount of a predetermined gas to each gas supply unit 6 so as to be supplied from the plurality of gas supply units 6 to the internal space 2I per unit time. The amount of gas can increase in the X direction. Thereby, in the substrate arrangement region 4R, the supply amount of the chalcogen element contained in the gas flowing per unit time in the space region of a predetermined size can be increased in the X direction. The concentration of the chalcogen element in a predetermined gas supplied from each gas supply source S6 to the corresponding gas supply unit 6 may be substantially constant.

  The space area of a predetermined size mentioned here may be a space area of a predetermined size in contact with one main surface of each heated substrate 5, for example. Specifically, for example, when each of the spatial regions is obtained by equally dividing one main surface of each heated substrate 5 into a plurality of regions (also referred to as divided regions), the divided regions are divided into the divided regions. As long as the space is within a predetermined distance in the normal direction of the divided area. Note that the one divided region may be, for example, a rectangular or square region whose one side is several μm or more and several tens of mm or less. The predetermined distance may be a distance of several μm or more and several mm or less, for example. The predetermined distance may be the same as the interval between two adjacent substrates to be heated 5 mounted on the cassette 4, for example. Moreover, the one main surface of the to-be-heated substrate 5 should just be the main surface by the side of -Y of the to-be-heated substrate 5, for example. Further, as the unit time, for example, an arbitrary time in the range of several seconds or more and tens of seconds or less can be adopted.

The plurality of gas discharge portions 7 are arranged in the X direction in the upper part of the internal space 2I. Moreover, what is necessary is just to make the space | interval of the adjacent gas exhaust parts 7 substantially constant, for example. In FIG. 1 and FIG. 2, reference numeral 71 is assigned to the gas discharge section 7 arranged _first from the −X side, and nth (here, n is an integer of 1 to 8) from the −X side. Reference numeral 7 _n is attached to the gas discharge section 7 arranged.

  Each gas discharge part 7 should just contain one or more tubular members. The internal space of each tubular member communicates with the internal space 2I of the heating furnace 2 through the opening 70. FIG. 2 shows an example in which each gas discharge portion 7 includes a plurality of tubular members and a plurality of openings 70. In this case, in each gas discharge part 7, the several opening 70 should just be arranged at the substantially constant space | interval in the Y direction.

The plurality of gas discharge adjustment units E7 adjust the discharge of gas from the internal space 2I by the plurality of gas discharge units 7. Each gas discharge adjustment part E7 should just have a pump, piping, a valve, etc. for exhaust, for example. In FIG. 1 and FIG. 2, the gas discharge adjusting unit E7 arranged _first from the −X side is denoted by E71 and is nth from the −X side (here, n is an integer of 1 to 8). Reference numeral E7 _n is attached to the gas discharge adjusting portion E7 disposed in the box.

Then, n-th gas exhaust adjusting unit E7 _n, are connected to the n-th gas discharge portion 7 _n, to adjust the discharge amount of the gas from the inner space 2I by n-th gas outlet portion 7 _n. Here, if the amount of gas discharged from the internal space 2I by the gas discharge unit 7 is large, a gas flow that supplements the gas discharge may occur in the internal space 2I. For this reason, for example, according to the amount of gas discharged per unit time from the internal space 2I by each gas discharge unit 7, the amount of chalcogen element contained in the gas flowing per unit time in each space region of a predetermined size in the substrate placement region 4R The supply amount can be adjusted. The gas is a gas supplied from the plurality of gas supply units 6 toward the substrate arrangement region 4R.

  In this case, for example, each gas discharge adjustment unit E7 adjusts the amount of gas discharged from the internal space 2I by each gas discharge unit 7 to thereby adjust the amount of gas discharged from the plurality of gas discharge units 7 per unit time. The amount can increase in the X direction. Thereby, in the substrate arrangement region 4R, the supply amount of the chalcogen element contained in the gas flowing per unit time in the space region of a predetermined size can be increased in the X direction. The supply amount of the predetermined gas from each gas supply unit 6 to the internal space 2I and the concentration of the chalcogen element in the predetermined gas may be substantially constant, for example.

  The heater 8 is wound around the heating furnace 2. By the heating by the heater 8, the plurality of heated substrates 5 arranged in the substrate arrangement region 4R of the internal space 2I can be heated substantially uniformly to a predetermined temperature in the range of 400 ° C. or higher and 600 ° C. or lower, for example. .

  The control unit C1 includes, for example, a processor, and controls the entire operation of the thin film manufacturing apparatus 1. For example, the control unit C1 supplies the gas from the plurality of gas supply sources S6 to the plurality of gas supply units 6, discharges the gas through the plurality of gas discharge units 7 by the plurality of gas discharge adjustment units E7, and the heater 8 The heating by the can be controlled.

<(1-2) Manufacture of photoelectric conversion device using thin film manufacturing apparatus>
Here, an example of a manufacturing process of the photoelectric conversion device 121 using the thin film manufacturing apparatus 1 having the above configuration will be described.

Here, the light absorption layer 131 as the semiconductor layer of the photoelectric conversion device 121 is formed using the thin film manufacturing apparatus 1. The light absorption layer 131 is a I-III-VI group compound semiconductor layer having a first conductivity type. Here, the first conductivity type may be a p-type conductivity type. The I-III-VI group compound semiconductor is a semiconductor mainly containing an I-III-VI group compound. Note that the semiconductor mainly containing the I-III-VI group compound means a semiconductor containing 70 mol% or more of the I-III-VI group compound. Also in the following description, “mainly included” means “70 mol% or more included”. I-III-VI group compounds mainly consist of group IB elements (also referred to as group 11 elements), group III-B elements (also referred to as group 13 elements), and group VI-B elements (also referred to as group 16 elements). It is a compound contained in. Examples of the I-III-VI group compound include CuInSe ₂ (also referred to as CIS), Cu (In, Ga) Se ₂ (also referred to as CIGS), and Cu (In, Ga) (Se, S) ₂ (also referred to as CIGSS). ) Etc. may be employed. Here, the light absorption layer 131 mainly contains CIGS.

  FIG. 4 is a flowchart illustrating a manufacturing flow of the photoelectric conversion device 121 using the thin film manufacturing apparatus 1. 5 to 12 are XY cross-sectional views schematically showing a state in the process of manufacturing the photoelectric conversion device 121. FIG. 13 is a plan view schematically showing the configuration of the photoelectric conversion device 121. FIG. 14 is a diagram showing an XY cross section at the position indicated by the alternate long and short dash line XIV-XIV in FIG. 13.

  First, in step Sp1 of FIG. 4, the substrate 101 is prepared. FIG. 5 is a diagram illustrating an example of the substrate 101. The substrate 101 supports a plurality of photoelectric conversion cells 110. As main materials included in the substrate 101, for example, glass, ceramics, resin, metal, and the like can be employed. The thickness of the substrate 101 may be about 1 mm or more and about 3 mm or less, for example.

  Next, in step Sp2, the lower electrode layer 102 is formed on substantially the entire surface of the cleaned substrate 101 by using a sputtering method or a vapor deposition method. FIG. 6 shows a state in which the lower electrode layer 102 is formed. The lower electrode layer 102 is a conductive layer provided on the −Y side main surface (also referred to as one main surface) of the substrate 101. As a main material included in the lower electrode layer 102, for example, various conductive metals such as Mo, Al, Ti, Ta, and Au can be adopted. Further, the thickness of the lower electrode layer 102 may be about 0.2 μm or more and about 1 μm or less, for example.

  In step Sp3, a groove portion P1 extending linearly in the Z direction is formed from a predetermined formation target position on the upper surface of the lower electrode layer 102 to the upper surface of the substrate 101 immediately below it. FIG. 7 shows a state after the groove portion P1 is formed. The groove P1 can be formed, for example, by irradiating a predetermined formation target position while scanning with a YAG laser or other laser light.

  In step Sp4, a raw material solution containing at least Cu, In and Ga, which are metal elements other than the chalcogen element contained in CIGS, and a solvent is applied from above the lower electrode layer 102 to form a film (raw material solution) as a first film. A film). Thereby, the substrate 101 on which the raw material solution is coated on one main surface is prepared. The thickness of the raw material solution film may be, for example, about several μm or more and about tens of μm or less.

  The raw material solution includes, for example, Cu as the IB group element, In and Ga as the III-B group element, and at least a metal complex of Cu, In, and Ga among Se as the VI-B group element as a solvent. Any dissolved solution may be used.

  Here, the raw material solution is a raw material solution in which a single source complex containing Cu, Ga, and a chalcogen element-containing organic compound as group IB elements is dissolved in a solvent (also referred to as a first raw material solution). ) May be employed. In addition, a single source complex is a complex compound which contains all the IB group element, the III-B group element, and the VI-B group element contained in the I-III-VI group compound. The single source complex functions as a precursor that can form a group I-III-VI compound by a chemical reaction of a group I-B element, a group III-B element, and a group VI-B element. For this reason, single source complexes are also referred to as single source precursors.

  The chalcogen element-containing organic compound is an organic compound containing a chalcogen element. Examples of the chalcogen element-containing organic compound include thiol, sulfide, disulfide, thiophene, sulfoxide, sulfone, thioketone, sulfonic acid, sulfonic acid ester, sulfonic acid amide, selenol, selenide, diselenide, selenoxide, selenone, tellurol, telluride, and ditelluride. Etc. may be employed. In particular, thiol, sulfide, disulfide, selenol, selenide, diselenide, tellurol, telluride, and ditelluride have high coordination power and easily form a stable complex with a metal element.

  When Cu is used as the IB group element and phenyl selenol is used as the chalcogen element-containing organic compound, the structure of the single source complex containing Ga includes, for example, the structure represented by the general formula (1). Can be employed. This single source complex can be prepared by the method shown in Patent Document 3 above. In addition, Ph in General formula (1) shows a phenyl group. If a polar solvent such as pyridine or aniline is employed as the solvent contained in the first raw material solution, the single source complex can be well dissolved by the solvent.

  Here, In is contained in the first raw material solution. For example, In may be contained in the first raw material solution in the form of a single source complex containing In. As the structure of the single source complex containing In, for example, the structure represented by the general formula (2) can be adopted.

  In step Sp5, the substrate 101 on which the raw material solution film is formed on one main surface is heated in an atmosphere containing at least one of moisture (specifically, water vapor) and oxygen. As a result, a drying process is performed on the raw material solution film disposed on the lower electrode layer 102 and in the groove portion P1, and a film as a second film in which the organic component in the raw material solution film is thermally decomposed (also called a dry film). Say) 130 may be formed. At this time, evaporation of the solvent contained in the raw material solution film and oxidation of a part of the metal element contained in the raw material solution film may occur. As a result, a dry film 130 containing a partially oxidized metal element can be formed on one main surface of the substrate 101. FIG. 8 shows a state in which the dry film 130 is formed.

  In addition, as the gas in the atmosphere at the time of thermal decomposition of the organic component, for example, a mixed gas of inert gas and water typified by nitrogen and argon, a mixed gas of reducing gas and water typified by hydrogen and the like, Alternatively, a mixed gas of an inert gas, a reducing gas, and water can be employed. Moreover, the heating temperature should just be 50 degreeC or more and 350 degrees C or less. The concentration of water in the gas including water may be, for example, 10 ppmv or more and 1000 ppmv or less. In particular, if the concentration of water is 50 ppmv or more and 150 ppmv or less, cracks are unlikely to occur in the dry film 130 during heating, and the dry film 130 is unlikely to peel from the lower electrode layer 102. Thereby, the light absorption layer 131 can be favorably crystallized by the heat treatment in step Sp8. As a result, the photoelectric conversion efficiency of the photoelectric conversion device 121 can be improved. Note that oxygen may be used in place of or in addition to water in the atmosphere gas during the thermal decomposition of the organic component.

  Further, during the thermal decomposition of the organic component, an oxide or the like may be generated by oxidizing a metal element or the like in the raw material solution film by at least one of moisture and oxygen in the atmosphere. For this reason, the dry film 130 may contain a certain amount of oxygen. And at the time of thermal decomposition of an organic component, metal elements, such as Ga, may become difficult to lose | disappear from a raw material solution film | membrane by heating a raw material solution film | membrane in the atmosphere containing at least one of a water | moisture content and oxygen. This makes it difficult for the ratio of the metal elements other than the chalcogen element in the dry coating 130 to deviate from a value close to the ratio of the metal elements other than the chalcogen element in the ideal CIGS. As a result, the light absorption layer 131 having high photoelectric conversion efficiency can be formed by performing the heat treatment of Step Sp8 on the dry film 130. In the dry film 130, some variation in the oxygen content may occur in the plane.

  By the way, as a factor that makes it difficult for a metal element such as Ga to disappear from the raw material solution film by heating the raw material solution film in an atmosphere containing at least one of moisture and oxygen during the thermal decomposition of the organic component, Several factors can be assumed. For example, Ga has a very low melting point compared to other Group IB metals and Group III-B metals. For this reason, when an organic component is thermally decomposed, it becomes easy to vaporize Ga by producing | generating liquid Ga. On the other hand, it can be assumed that the presence of at least one of moisture and oxygen in the atmosphere in which the organic component is thermally decomposed forms Ga oxides and the like, thereby suppressing Ga vaporization.

  Here, the processes of steps Sp <b> 1 to Sp <b> 5 are performed on a plurality of substrates 101, whereby a plurality of heated objects in which the lower electrode layer 102 and the dry film 130 are respectively stacked on one main surface of the substrate 101. A substrate 5 can be prepared. In other words, a plurality of heated substrates 5 each having a dry film 130 disposed on one main surface can be prepared. The dry film 130 contains at least a metal element other than the chalcogen element contained in CIGS as a compound semiconductor mainly contained in the light absorption layer 131.

  In step Sp6, the in-plane distribution of the oxygen content is obtained for the dry film 130 of each substrate to be heated 5. For example, the in-plane distribution of the oxygen content may be acquired by obtaining the oxygen content for each divided region.

  For example, among the plurality of heated substrates 5 prepared in Step Sp5, the dry film 130 disposed on another heated substrate 5 different from the two or more heated substrates 5 used in the processes after Step Sp7. The target oxygen concentration and thickness may be measured. If the oxygen concentration and thickness in each divided region of the dry film 130 are known, the volume of each divided region is uniquely determined, and the oxygen content in each divided region is determined based on the volume and oxygen concentration. obtain.

  The measurement of the oxygen concentration in the dry film 130 can be realized by, for example, secondary ion mass spectrometry (SIMS). Further, the thickness of the dry film 130 can be measured by a film thickness measuring device using X-rays, a film thickness meter, a reflection interferometer, or the like. For example, based on the measurement result, the in-plane distribution of the oxygen content related to the dry film 130 of the two or more substrates to be heated 5 can be measured.

  In addition, when the thickness of the dry film 130 is set to a substantially uniform predetermined value, even if the thickness of the dry film 130 is not measured, if the oxygen concentration is measured for the dry film 130, the dry film 130 is dried. The oxygen content in each divided region of the film 130 can be uniquely determined. From another viewpoint, when the thickness of the dry film 130 is set to a substantially uniform predetermined value, the oxygen concentration in each divided region can indirectly indicate the oxygen content in each divided region.

  Here, the dry film 130 disposed on the heated substrate 5 to be measured and the other dry film 130 formed under substantially the same conditions as the dry film 130 have substantially the same oxygen content. An internal distribution can be realized. For this reason, the in-plane distribution of the oxygen content obtained by the measurement for the other dry film 130 is the dry film 130 disposed on the two or more heated substrates 5 used in the processes after Step Sp7. Can be employed as the in-plane distribution of oxygen content. In this case, for reducing or avoiding damage to the dry film 130 by physical measurement for two or more heated substrates 5 used in the processes after Step Sp7, and for obtaining the oxygen content of the dry film 130 The time required for measurement can be shortened.

  In step Sp7, two or more predetermined numbers of the substrates to be heated 5 are arranged in the cassette 4, and the cassette 4 is arranged in the heating furnace 2 of the thin film manufacturing apparatus 1, so that the predetermined number of the substrates to be heated 5 are arranged. Arranged in the substrate placement region 4R. Here, the predetermined number of heated substrates 5 of 2 or more may be all the heated substrates 5 among the plurality of heated substrates 5 prepared in Steps Sp1 to Sp5, or a part of the heated substrates. The substrate 5 may be used. Here, for example, seven substrates to be heated 5 are arranged. At this time, the in-plane distribution of the oxygen content for each dry film 130 in the predetermined number of substrates to be heated 5 equal to or greater than two may be substantially the same. The two or more predetermined numbers of the substrates to be heated 5 can be prepared by performing the processes of Steps Sp1 to Sp5 under substantially the same conditions.

  In step Sp8, the thin film manufacturing apparatus 1 performs heat treatment on two or more substrates to be heated 5. The heat treatment may be performed in an atmosphere containing a chalcogen element gas and a non-oxidizing gas. Specifically, the supply amount of the chalcogen element per unit time varies in each space region of a predetermined size in contact with each dry film 130 according to the in-plane distribution of the oxygen content for each dry film 130. A gas containing a chalcogen element is caused to flow through. For example, regarding the supply amount of the chalcogen element per unit time for each spatial region, if the minimum amount is 1, the maximum amount may be increased to about 1.5. Thereby, during the heat treatment, unnecessary oxygen can be replaced with the chalcogen element in each dry film 130. For this reason, in each dry membrane | film | coat 130, oxygen content can be reduced substantially uniformly and content of a chalcogen element can be raised substantially uniformly. That is, the light absorption layer 131 having high photoelectric conversion efficiency can be formed. As a result, the photoelectric conversion efficiency in the photoelectric conversion device 121 can be improved.

  Here, for example, at least one of supply of a predetermined gas containing a chalcogen element to the internal space 2I by the plurality of gas supply units 6 and exhaust from the internal space 2I by the plurality of gas discharge units 7 is adjusted. The Thereby, the supply amount of the chalcogen element contained in the gas flowing per unit time in each space region of a predetermined size can be adjusted.

  The supply of the predetermined gas to the internal space 2I may be adjusted, for example, by adjusting the supply amount of the predetermined gas per unit time to the internal space 2I by each gas supply unit 6. Thereby, supply of the predetermined gas to the internal space 2I by the plurality of gas supply units 6 can be easily adjusted.

  Specifically, for example, among the plurality of gas supply units 6, a predetermined gas supply amount by the gas supply unit 6 disposed near a portion having a relatively high oxygen content in each dry film 130 is relatively It only has to be enhanced. In other words, among the plurality of gas supply units 6, a predetermined gas supply amount by the gas supply unit 6 disposed near a portion having a relatively low oxygen content in each dry film 130 is relatively reduced. It should be done. And when the oxygen content about each dry membrane | film | coat 130 shows the tendency to increase, so that it goes to + X direction, the supply_amount | feed_rate to the internal space 2I of the predetermined | prescribed gas per unit time by the several gas supply part 6 is the following. What is necessary is just to raise according to the arrangement | sequence order of this + X direction of these gas supply parts 6. FIG.

  Further, the adjustment of the exhaust from the internal space 2I may be, for example, an adjustment of the exhaust amount of gas per unit time from the internal space 2I by each gas discharge unit 7. Thereby, the discharge | emission of the gas from the internal space 2I by the some gas discharge part 7 can be adjusted easily.

  Specifically, for example, among the plurality of gas discharge units 7, the amount of gas discharged by the gas discharge unit 7 disposed near the portion having a relatively high oxygen content in each dry film 130 is relatively It only has to be raised. In other words, among the plurality of gas discharge units 7, the amount of gas discharged by the gas discharge unit 7 disposed near the portion having a relatively low oxygen content in each dry film 130 is relatively reduced. It ’s fine. And when the oxygen content about each dry film 130 shows the tendency to increase, so that it goes to the + X direction, the discharge | emission amount of the gas from the internal space 2I per unit time by several gas discharge part 7 is this plurality. What is necessary is just to raise according to the arrangement | sequence order of the + X direction of the gas discharge part 7 of this.

  Moreover, the heat processing temperature in heat processing should just be 400 degreeC or more and 600 degrees C or less, for example. And by this heat processing, crystallization of CIGS in each dry film 130 advances, and the light absorption layer 131 which mainly contains CIGS may be formed. As a result, the two or more substrates to be heated 5 become the processed substrates 150 in which the good and uniform light absorption layers 131 are respectively disposed on the substrate 101.

  In addition, about the supply_amount | feed_rate of the gas per unit time to the internal space 2I by the some gas supply part 6, the optimal supply_amount | feed_rate can be set based on the experimental result using the thin film manufacturing apparatus 1, for example. Specifically, for example, the supply amount of a predetermined gas per unit time to the internal space 2I by the plurality of gas supply units 6, the in-plane distribution of the oxygen content for each substrate to be heated 5, and each processed substrate According to the relationship with the in-plane distribution of the CIGS composition at 150, an optimum supply amount can be set.

  Moreover, about the discharge | emission amount of the gas per unit time from the internal space 2I by the some gas discharge part 7, the optimal discharge | emission amount may be set based on the experimental result using the thin film manufacturing apparatus 1, for example. Specifically, for example, the amount of gas discharged per unit time from the internal space 2 </ b> I by the plurality of gas discharge units 7, the in-plane distribution of the oxygen content for each heated substrate 5, and the post-processing substrate 150 The optimal discharge amount can be set according to the relationship with the in-plane distribution of the CIGS composition.

  In step Sp9, subsequent steps in the manufacturing process of the photoelectric conversion device 121 are performed. Here, an example of the subsequent steps will be described.

  First, the buffer layer 132 is formed on the light absorption layer 131 formed in Step Sp8. The buffer layer 132 mainly includes a semiconductor having a second conductivity type different from the first conductivity type of the light absorption layer 131. Here, the second conductivity type may be an n-type conductivity type. The buffer layer 132 may be formed by a chemical bath deposition method (CBD method). For example, the buffer layer 132 mainly containing CdS can be formed by immersing the light absorption layer 131 in a solution prepared by dissolving cadmium acetate and thiourea in aqueous ammonia. Thereby, the photoelectric conversion layer 103 in which the light absorption layer 131 and the buffer layer 132 are laminated can be formed. FIG. 9 shows a state where the photoelectric conversion layer 103 is formed.

  Next, a groove portion P <b> 2 extending linearly in the Z direction is formed in a region from a predetermined formation target position on the upper surface of the buffer layer 132 to the upper surface of the lower electrode layer 102. FIG. 10 shows a state after the groove portion P2 is formed. The groove portion P2 can be formed by mechanical scribing or the like using a scribe needle.

  Next, the upper electrode layer 104 is formed from the upper surface of the photoelectric conversion layer 103 to the inside of the groove portion P2. FIG. 11 shows a state after the upper electrode layer 104 is formed. The upper electrode layer 104 can be formed by a sputtering method, a vapor deposition method, a chemical vapor deposition (CVD) method, or the like. For example, the upper electrode layer 104 as a transparent conductive film mainly containing ZnO to which Al is added is formed on the buffer layer 132. At this time, a hanging portion (also referred to as a hanging portion) 104a of the upper electrode layer 104 is formed in the groove portion P2.

  Next, the collector electrode 105 is formed from a predetermined formation target position on the upper surface of the upper electrode layer 104 to the inside of the groove portion P2. FIG. 12 shows a state after the current collecting electrode 105 is formed. The collecting electrode 105 is a linear electrode portion provided on one main surface of the upper electrode layer 104. The current collecting electrode 105 includes a plurality of current collecting portions 105a, a connecting portion 105b, and a hanging portion 105c. The collector electrode 105 is printed by, for example, a metal paste in which a metal powder such as silver is dispersed in a resin binder or the like having a predetermined pattern, and the printed metal paste is solidified by drying. Can be formed.

  After the current collecting electrode 105 is formed, a groove portion P3 extending linearly in the Z direction is formed in a region from a predetermined formation target position on the upper surface of the upper electrode layer 104 to the upper surface of the lower electrode layer 102. It is formed. Thereby, a photoelectric conversion device 121 in which a plurality of photoelectric conversion cells 110 are arranged on the substrate 101 shown in FIGS. 13 and 14 is obtained. The groove part P3 can be formed by mechanical scribing or the like using a scribe needle, like the groove part P2.

  As shown in FIGS. 13 and 14, the plurality of current collectors 105a are separated in the Z-axis direction, and each current collector 105a extends in the X-axis direction. The connection part 105b is extended in the Z-axis direction, and each current collection part 105a is connected. The hanging portion 105c is connected to the lower portion of the connecting portion 105b and is disposed in the groove portion P2. Here, the connecting portion 145 including the hanging portion 105c and the hanging portion 104a is connected to the lower electrode layer 102 extended from the adjacent photoelectric conversion cell 110 through the groove portion P2. That is, in the photoelectric conversion device 121, a plurality of photoelectric conversion cells 110 arranged on the substrate 101 are electrically connected in series. Although two photoelectric conversion cells 110 are illustrated in FIGS. 13 and 14, a predetermined number of three or more photoelectric conversion cells 110 may be arranged in the X direction in the photoelectric conversion device 121.

<(1-3) Manufacture of photoelectric conversion device including measurement of in-plane distribution of oxygen content>
FIG. 15 is a flowchart illustrating the manufacturing flow of the photoelectric conversion device 121 using the thin film manufacturing apparatus 1 including measurement of the in-plane distribution of oxygen content for the dry film 130.

  In steps ST1 to ST5, processing similar to that in steps Sp1 to Sp5 in FIG. 4 is performed.

  Specifically, in step ST1, another substrate 101 different from the two or more substrates 101 used for manufacturing the photoelectric conversion device 121 in step ST7 is prepared. Next, the lower electrode layer 102 is formed on one main surface of the substrate 101 prepared in step ST1 (step ST2), and a groove P1 is formed from the upper surface of the lower electrode layer 102 to the upper surface of the substrate 101 (step ST3). ). Next, the substrate 101 on which the lower electrode layer 102 and the groove P1 are formed is targeted, and a raw material solution is applied on the lower electrode layer 102 and in the groove P1 on one main surface of the substrate 101 (step ST4). Thereby, the board | substrate with which the raw material solution membrane | film | coat as a 3rd membrane | film | coat is distribute | arranged can be formed.

  Thereafter, the substrate is heated in an atmosphere containing at least one of moisture and oxygen, whereby a drying process is performed on the raw material solution film, and the organic film in the raw material solution film is thermally decomposed. As a result, a dry film 130 is formed (step ST5). At this time, evaporation of the solvent contained in the raw material solution film and oxidation of a part of the metal element contained in the raw material solution film may occur. As a result, a dry film 130 containing a partially oxidized metal element can be formed on one main surface of the substrate 101. As a result, a measurement substrate (also referred to as a measurement substrate) on which the dry film 130 is disposed can be formed in the same manner as the heated substrate 5.

  In step ST6, the in-plane distribution of oxygen content is measured for the dry film 130 on the measurement substrate. That is, the oxygen content is measured for the dry film 130 provided on another substrate 101 different from the two or more substrates 101 used for manufacturing the photoelectric conversion device 121 in step ST7. And based on this measurement result, in-plane distribution of oxygen content about each dry coat 130 arranged on the two or more substrates can be acquired, respectively.

  Here, for example, the dry film 130 of the measurement substrate may be targeted by secondary ion mass spectrometry (SIMS), and the oxygen concentration may be measured for each divided region. Further, the thickness of the dry film 130 may be measured by, for example, a film thickness measuring device using X-rays, a film thickness meter, a reflection interferometer, or the like. Thereby, the in-plane distribution of the oxygen content in the dry film 130 can be measured. If the thickness of the dry film 130 is a substantially uniform predetermined value, the in-plane distribution of the oxygen content in the dry film 130 can be measured by measuring the in-plane distribution of the oxygen concentration for the dry film 130. .

  In step ST7, the photoelectric conversion device 121 is manufactured using the thin film manufacturing apparatus 1 shown in FIG. In this case, in step Sp6 of FIG. 4, the in-plane distribution of the oxygen content measured in the process of step ST6 performed recently is the surface of the oxygen content for the dry film 130 of each substrate 5 to be heated. Obtained as internal distribution.

  In step ST8, it is determined whether or not the specification of the raw material solution used in step Sp4 in FIG. 4 is changed. If the specification of the raw material solution has not been changed, the process proceeds to step ST9. If the specification of the raw material solution has been changed, the process returns to step ST1. Here, if the specifications of the raw material solution are changed, the viscosity and the like of the raw material solution may be different. For this reason, the thickness etc. of the raw material solution film | membrane formed by application | coating of a raw material solution may change. That is, the specification of the raw material solution film as the first film can be changed. As a result, the in-plane distribution of the oxygen content in the dry film 130 can change. Therefore, every time the specification of the raw material solution is changed, the processing in steps ST1 to ST6 is performed again, whereby the in-plane distribution of the oxygen content in the dry film 130 is measured. Thereby, the reliability of the in-plane distribution of the oxygen content for the dry film 130 obtained in step Sp6 of FIG. 4 can be increased.

  In step ST9, it is determined whether or not there is a change in at least one of the coating apparatus used in step Sp4 and the drying apparatus used in step Sp5. Here, if neither the coating apparatus nor the drying apparatus has been changed, the process proceeds to step ST10. If at least one of the coating apparatus and the drying apparatus is changed, the process returns to step ST1.

  Here, if the coating apparatus is changed, the distribution of the thickness of the raw material solution film formed by the application of the raw material solution may change. Further, if the drying apparatus is changed, for example, the degree of oxidation of the metal element in the raw material solution film can be changed. As a result, the in-plane distribution of the oxygen content in the dry film 130 can change. Therefore, the in-plane distribution of the oxygen content in the dry film 130 is measured by performing the processing of steps ST1 to ST6 again for each combination of the coating apparatus and the drying apparatus. Thereby, the reliability of the in-plane distribution of the oxygen content for the dry film 130 obtained in step Sp6 of FIG. 4 can be increased.

  In addition, whenever the specification of at least one of the coating apparatus and the drying apparatus is changed, the processes of steps ST1 to ST6 may be performed again. In other words, the in-plane distribution of the oxygen content in the dry film 130 may be measured by performing the processing of steps ST1 to ST6 again for each combination of specifications of the coating apparatus and the drying apparatus. In this case, the frequency of measuring the in-plane distribution of oxygen content is reduced. As a result, the production efficiency of the photoelectric conversion device 121 can be improved.

  In step ST10, it is determined whether or not the manufacture of the photoelectric conversion device 121 is continued. Here, if manufacture of the photoelectric conversion apparatus 121 is continued, it will return to step ST7. Further, if the production of the photoelectric conversion device 121 is not continued, this operation flow is ended.

<(1-4) Summary of One Embodiment>
As described above, in this embodiment, the substrate 101 on which the raw material solution film is formed on one main surface by applying the raw material solution is heated in an atmosphere containing at least one of moisture and oxygen. Thereby, the dry film 130 containing the metal element in which the organic component in the raw material solution film is thermally decomposed and partially oxidized can be formed. This makes it difficult for the ratio of the metal elements other than the chalcogen element in the dry coating 130 to deviate from a value close to the ratio of the metal elements other than the chalcogen element in the ideal CIGS.

  Further, two or more heated substrates 5 each having a dry film 130 disposed on one main surface are disposed in the heating furnace 2. In the heating furnace 2, two or more substrates to be heated 5 are heated. During this heat treatment, the supply amount of the chalcogen element per unit time varies depending on the in-plane distribution of the oxygen content of each dry film 130 in each space region of a predetermined size in contact with each dry film 130. Thus, a gas containing a chalcogen element is flowed. Thereby, during the heat treatment, unnecessary oxygen can be replaced with the chalcogen element in each dry film 130. For this reason, in each dry membrane | film | coat 130, oxygen content can be reduced substantially uniformly and content of a chalcogen element can be raised substantially uniformly. That is, the light absorption layer 131 having high photoelectric conversion efficiency can be formed. As a result, the photoelectric conversion efficiency in the photoelectric conversion device 121 can be improved.

  Furthermore, two or more light absorption layers 131 are formed by heat-treating two or more substrates to be heated 5 at one time in one heating furnace 2. For this reason, a uniform thin film of a compound semiconductor containing a chalcogen element can be produced in large quantities. As a result, the photoelectric conversion device 121 having high photoelectric conversion efficiency can be easily mass-produced.

<(2) Modification>
Note that the present invention is not limited to the above-described embodiment, and various modifications and improvements can be made without departing from the gist of the present invention.

<(2-1) First Modification>
In the one embodiment, for example, by adjusting the gas discharge amount per unit time from the internal space 2I by each gas discharge unit 7, the chalcogen element contained in the gas flowing per unit time in each space region of a predetermined size Although supply amount was adjusted, it is not restricted to this. For example, the density of the chalcogen elements contained in the gas flowing per unit time in each space region of a predetermined size, depending on the density (also referred to as arrangement density) in which a plurality of gas discharge portions 7 that discharge gas from the internal space 2I are arranged. The supply amount may be adjusted.

  Specifically, for example, in the thin film manufacturing apparatus 1, the gas in the internal space 2 </ b> I is discharged by some of the plurality of gas discharge units 7 by the plurality of gas discharge adjustment units E <b> 7. It only has to be adjusted to. For example, when the oxygen content in each dry film 130 tends to increase as it goes in the + X direction, the arrangement density of the plurality of gas discharge units 7 that discharge gas from the internal space 2I is increased in the + X direction. It only has to be done.

FIG. 16 shows how the gas in the internal space 2I is discharged through the corresponding gas discharge part 7 by opening the valve of the gas discharge adjustment part E7 that is hatched with diagonal lines. FIG. 16 shows how the gas in the internal space 2I is discharged through the _third , _fifth , _seventh , and _eighth gas discharge portions 7 ₃ , 7 ₅ , 7 ₇ , and 7 ₈ . In this case, the amount of gas discharged per unit time from the internal space 2I through the gas discharge units 7 ₃ , 7 ₅ , 7 ₇ and 7 ₈ is made substantially constant by the control by the control unit C1, for example. Also good.

  Note that the arrangement density of the plurality of gas discharge units 7 that discharge gas from the internal space 2I can be set to an optimum arrangement density based on the experimental results in which the thin film manufacturing apparatus 1 is used. Further, among the plurality of gas discharge adjustment units E7 and the plurality of gas discharge units 7, the gas discharge adjustment unit E7 and the gas discharge unit 7 that are not used for discharging the gas from the internal space 2I may be omitted.

<(2-2) Second Modification>
In the above embodiment, for example, by adjusting the supply amount of a predetermined gas per unit time to the internal space 2I by each gas supply unit 6, the chalcogen contained in the gas flowing per unit time in each space region of a predetermined size Although the supply amount of the element has been adjusted, the present invention is not limited to this. For example, the density of the chalcogen elements contained in the gas flowing per unit time in each space region of a predetermined size depending on the density (also referred to as arrangement density) in which a plurality of gas supply units 6 that supply gas to the internal space 2I are arranged. The supply amount may be adjusted.

  Specifically, for example, in the thin film manufacturing apparatus 1, a predetermined gas is supplied to the internal space 2I by a part of the plurality of gas supply units 6 by the plurality of gas supply sources S6. It only has to be adjusted to. For example, when the oxygen content in each dry film 130 tends to increase as it goes in the + X direction, the arrangement density of the plurality of gas supply units 6 that supply a predetermined gas to the internal space 2I is + X. It only has to be raised in the direction.

FIG. 17 shows a state in which a predetermined gas is supplied to the internal space 2I by the corresponding gas supply unit 6 by opening the valve of the gas supply source S6 that is hatched with diagonal lines. Specifically, FIG. 17 shows a state in which a predetermined gas is supplied to the internal space 2I by the _third , _fifth , _seventh and _eighth gas supply units 6 ₃ , 6 ₅ , 6 ₇ and 6 ₈ . Yes. In this case, for example, the amount of gas supplied per unit time to the internal space 2I by the gas supply units 6 ₃ , 6 ₅ , 6 ₇ and 6 ₈ may be made substantially constant by the control by the control unit C1. .

  The arrangement density of the plurality of gas supply units 6 that supply a predetermined gas to the internal space 2I can be set to an optimum arrangement density based on the experimental result in which the thin film manufacturing apparatus 1 is used. Of the plurality of gas supply sources S6 and the plurality of gas supply units 6, the gas supply source S6 and the gas supply unit 6 that are not used for supplying a predetermined gas to the internal space 2I may be omitted.

<(2-3) Third Modification>
In the above embodiment, the supply amount of the chalcogen element per unit time differs in each space region of a predetermined size in contact with each dry film 130 according to the in-plane distribution of the oxygen content in each dry film 130. Although the gas containing a chalcogen element was flowed, it is not limited to this. For example, a gas containing a chalcogen element is caused to flow in a space region of a predetermined size in contact with each dry film 130 so that the supply amount of the chalcogen element per unit time varies depending on the oxygen content of each dry film 130. May be. In the following, in the third modified example, differences from the above embodiment will be mainly described.

  For example, as shown in FIG. 18, the cassette 4 disposed in the internal space 2I of the thin film manufacturing apparatus 1 may be changed to a cassette 4A. Further, in FIG. 19, similarly to FIG. 2, an XY cross section of the heating furnace 2 and the heater 8, a plurality of gas discharge units 7, and a plurality of gas discharge adjustment units E <b> 7 are schematically illustrated. 20, similarly to FIG. 3, an XY cross section of the heating furnace 2 and the heater 8, a plurality of gas supply units 6, and a plurality of gas supply sources S6 are schematically shown.

  As shown in FIGS. 18 to 20, the cassette 4A is loaded with a predetermined number of heated substrates 2A of 2 or more arranged in the X direction. Here, the predetermined number of 2 or more is 8. In the cassette 4A, the main surfaces of the front and back surfaces of each heated substrate 5A are substantially parallel to the YZ plane. In other words, the adjacent substrates to be heated 5A face each other. Moreover, the space | interval of the adjacent to-be-heated board | substrates 5A with which the cassette 4A is mounted should just be made substantially constant, for example. Furthermore, the substrate to be heated 5A only needs to have substantially the same configuration as the substrate to be heated 5 according to the embodiment.

  In addition, about FIGS. 5-14 which show the state in the middle of manufacture of the photoelectric conversion apparatus 121, and a completed product, if an X-axis, a Y-axis, and a Z-axis are each substituted by a Z-axis, an X-axis, and a Y-axis, for example good. The manufacturing flow of the photoelectric conversion device 121 and the manufacturing flow of the photoelectric conversion device 121 using the thin film manufacturing device 1 including the measurement of the in-plane distribution of the oxygen content for the dry film 130 are shown in FIGS. 4 and 15. A flow similar to that of the above-described embodiment shown in FIG.

In FIG. 18 to FIG. 20, reference numeral 5 </ b> A ₁ is assigned to the substrate 5 to be heated _first from the −X side, and nth (here, n is an integer of 1 to 8) from the −X side. code 5A _n is attached to the heated substrate 5A. The cassette 4A mainly includes twelve frames that are connected to each other and surround a substantially rectangular parallelepiped substrate arrangement region 4R on which two or more heated substrates 5A are arranged. 18 to 20, the outer edge of the cassette 4A is indicated by a one-dot chain line.

Here, as shown in FIG. 19, when viewed from the −Z side, for example, the n-th heated substrate 5 _</ b _{> A} n is more than the n-th (n is an integer of 1 to 8) gas discharge unit 7 _n. Slightly placed on the + X side. In other words, when viewed from the -Z side, for example, n-th of the heated substrate 5A _n is disposed between the n-th gas outlet portion 7 _n and n + 1 th gas outlet portion 7 _{n + 1} . Further, as shown in FIG. 20, when viewed from the + Z side, for example, the n-th (n is an integer of 1 to 8) heated substrate 5A _n is slightly more + X than the n-th gas supply unit 6 _n. Arranged on the side. In other words, + when viewed from the Z-side, for example, n-th of the heated substrate 5A _n is disposed between the n-th gas supply unit 6 _n and n + 1 th gas supply section 6 _{n + 1.}

  When the heat treatment is performed on the two or more substrates to be heated 5A, the chalcogen element is supplied to each space region of a predetermined size so that the supply amount of the chalcogen element per unit time varies depending on the oxygen content of each dry film 130. It is sufficient that a gas containing is flowed.

  The space area of a predetermined size mentioned here may be a space area of a predetermined size in contact with one principal surface of the −X side of each heated substrate 5A, for example. Specifically, the space area of a predetermined size may be a space that is within a range of a predetermined distance in the normal direction of the one main surface from the one main surface on the −X side of each heated substrate 5A, for example. More specifically, the predetermined size may be, for example, the size of a space positioned between adjacent heated substrates 5A. Further, as the unit time, for example, an arbitrary time in the range of several seconds or more and tens of seconds or less can be adopted.

  By adopting such a configuration, the oxygen content in the plurality of dry coatings 130 is reduced substantially uniformly and the chalcogen element content is reduced despite the variation in oxygen content in the plurality of dry coatings 130. It can be increased substantially uniformly. That is, a plurality of light absorption layers 131 having high photoelectric conversion efficiency can be formed respectively. As a result, a large number of photoelectric conversion devices 121 with high photoelectric conversion efficiency can be produced.

  In the present modification, as in the above-described embodiment, for example, the supply of a predetermined gas containing a chalcogen element to the internal space 2I by the plurality of gas supply units 6 and the inside by the plurality of gas discharge units 7 are performed. At least one of the exhaust from the space 2I is adjusted. Thereby, the supply amount of the chalcogen element contained in the gas flowing per unit time in each space region of a predetermined size can be adjusted.

  Regarding the adjustment of the supply of the predetermined gas to the internal space 2I, the adjustment of the supply of the predetermined gas to the internal space 2I in at least one of the embodiment and the second modification may be employed. Thereby, supply of the predetermined gas to the internal space 2I by the plurality of gas supply units 6 can be easily adjusted.

  Specifically, for example, among the plurality of gas supply units 6, a predetermined gas by the gas supply unit 6 disposed near the dry film 130 having a relatively high oxygen content among the plurality of dry films 130. As long as the supply amount is relatively increased. In other words, among the plurality of gas supply units 6, a predetermined gas supply amount by the gas supply unit 6 disposed near the dry film 130 having a relatively low oxygen content among the plurality of dry film 130. Should be relatively reduced. For example, when the oxygen content of the plurality of dry coatings 130 tends to increase as it goes in the + X direction, the supply amount of a predetermined gas per unit time by the plurality of gas supply units 6 is the plurality of gas supply units. What is necessary is just to raise according to the arrangement | sequence order of the + X direction of the part 6. FIG.

  Further, regarding the adjustment of the exhaust from the internal space 2I, the adjustment of the exhaust in at least one of the one embodiment and the first modification may be employed. Thereby, the discharge | emission of the gas from the internal space 2I by the some gas discharge part 7 can be adjusted easily.

  Specifically, for example, gas discharge by the gas discharge unit 7 disposed near the dry film 130 having a relatively high oxygen content among the plurality of dry films 130 among the plurality of gas discharge units 7. It is sufficient that the amount is relatively increased. In other words, among the plurality of gas discharge units 7, the amount of gas discharged by the gas discharge unit 7 disposed near the dry film 130 having a relatively low oxygen content among the plurality of dry films 130 is relative. It is sufficient if it is reduced. For example, when the oxygen content of the plurality of dry coatings 130 tends to increase as it goes in the + X direction, the amount of gas discharged per unit time by the plurality of gas discharge units 7 is the plurality of gas discharge units 7. It may be improved according to the arrangement order in the + X direction.

<(2-4) Other modifications>
For example, in the one embodiment and the first to third modifications, the light absorption layer 131 includes the I-III-VI group compound semiconductor, but the invention is not limited thereto. For example, the compound semiconductor included in the light absorption layer 131 may be a compound semiconductor including a chalcogen element. As a compound semiconductor containing a chalcogen element, for example, an I-II-IV-VI group compound semiconductor (CZTS) mainly containing four elements of Cu, Zn, Sn, and S, and two elements of Cd and Te are mainly contained. II-VI group compound semiconductors can be employed. That is, the present invention can be applied to a general technique for manufacturing a compound semiconductor thin film containing a chalcogen element.

  In the one embodiment and the first to third modifications, the adjustment of the supply of the predetermined gas to the internal space 2I is, for example, a predetermined unit time per unit time to the internal space 2I by each gas supply unit 6 Although it was adjustment of the supply_amount | feed_rate of gas, it is not restricted to this. For example, depending on the concentration of the chalcogen element in a predetermined gas supplied into the one heating furnace 2 by each gas supply unit 6, it is included in the gas flowing per unit time in each space region of a predetermined size in the substrate arrangement region 4 </ b> R. The supply amount of the chalcogen element may be adjusted.

  For example, the plurality of gas supply sources S6 supply gases having different concentrations of chalcogen elements to the plurality of gas supply units 6, so that the predetermined gas supplied from the plurality of gas supply units 6 to the internal space 2I The concentration of the chalcogen element can increase in the X direction. Thereby, in the substrate arrangement region 4R, the supply amount of the chalcogen element contained in the gas flowing per unit time in the space region of a predetermined size can be increased in the X direction. In this case, for example, the supply amount of the predetermined gas supplied from each gas supply source S6 to the corresponding gas supply unit 6 per unit time may be substantially constant.

  Also, in the one embodiment and the first and second modifications, the oxygen content of each dry film 130 in the two or more predetermined number of substrates to be heated 5 arranged in one heating furnace 2 is in-plane. The distributions are substantially the same as each other, but the present invention is not limited to this. For example, if at least one of adjustment of supply of a predetermined gas through each opening 60 and adjustment of gas discharge through each opening 70 can be adjusted, in-plane distribution of oxygen content for each dry film 130 May not be substantially identical to each other. In this case, the gas containing the chalcogen element can be flowed so that the supply amount of the chalcogen element per unit time varies depending on the in-plane distribution of the oxygen content for each dry film 130.

  In the one embodiment and the first and second modifications, two or more predetermined numbers of the substrates to be heated 5 are arranged in one direction in the cassette 4, but the present invention is not limited to this. For example, the cassette 4 may be provided with one or more heated substrates 5. Even with such a configuration, in one dry film 130, the oxygen content can be reduced substantially uniformly, and the content of the chalcogen element can be increased substantially uniformly. For this reason, the light absorption layer 131 with high photoelectric conversion efficiency is formed, and the photoelectric conversion efficiency in the photoelectric conversion apparatus 121 can be improved.

  In the one embodiment and the first to third modifications, the raw material solution film as the first film and the third film is formed by applying the raw material solution. However, the present invention is not limited to this. Instead of the raw material solution film, the first film and the third film as the third film containing at least a metal element other than the chalcogen element contained in the compound semiconductor containing the chalcogen element are formed by, for example, sputtering or vapor deposition. It may be formed on the layer 102. In this case, for example, the raw material film is heated in an atmosphere containing at least one of moisture and oxygen, thereby causing a part of the metal element to be oxidized. What is necessary is just to form the to-be-heated film as a 4th film | membrane.

  It goes without saying that all or a part of each of the above-described embodiment and various modifications can be appropriately combined within a consistent range.

  Examples of the present invention will be described below, but the present invention is not limited thereto.

<(A) Preparation of raw material solution>
The raw material solution was prepared by performing the following steps [A1] to [A4].

[A1] 10 mmol of Cu (CH ₃ CN) ₄ .PF ₆ and 20 mmol of P (C ₆ H ₅ ) ₃ were dissolved in 100 ml of acetonitrile to form a first solution. And the 1st complex solution was prepared by stirring this 1st solution at 25 degreeC as room temperature for 5 hours.

[A2] 40 mmol of NaOCH ₃ and 40 mmol of HSeC ₆ H ₅ which is a chalcogen element-containing organic compound were dissolved in 300 ml of methanol to form a second solution. Further, 6 mmol of InCl ₃ and 4 mmol of GaCl ₃ were dissolved in the second solution, thereby generating a third solution. Then, the second complex solution was prepared by stirring the third solution at room temperature for 5 hours.

  [A3] The second complex solution prepared in the step [A2] was added dropwise to the first complex solution prepared in the step [A1], thereby generating a white precipitate (precipitate). The precipitate is extracted, washed with methanol, and then dried at room temperature, so that the precipitate contains a mixture of the single source precursors represented by the general formula (1) and the general formula (2). Things were obtained. In this mixture of single source precursors, one complex molecule includes Cu, Ga, and Se, or includes Cu, In, and Se.

  [A4] By adding pyridine as an organic solvent to the precipitate containing the mixture of the single source precursors obtained in the above step [A3], the concentration of the single source precursor is 45% by mass. A raw material solution was made.

<(B) Production of Semiconductor Layer According to Example>
A substrate 101 mainly containing glass was prepared. The substrate 101 had a rectangular main surface with a long side of 800 mm and a short side of 500 mm. Next, a lower electrode layer 102 mainly containing Mo was formed on one main surface of the substrate 101. Next, from the upper surface of the lower electrode layer 102 to the upper surface of the substrate 101, eight groove portions P <b> 1 substantially parallel to the short side of the main surface of the substrate 101 are aligned along the long side of the main surface of the substrate 101. Formed at intervals. Further, a raw material solution was applied to the upper surface of the lower electrode layer 102 by a blade method in an atmosphere of nitrogen gas, thereby forming a raw material solution film having a substantially uniform thickness.

  Next, the raw material solution film is heated at about 300 ° C. for about 10 minutes in an atmosphere of nitrogen gas containing moisture, whereby the raw material solution film is dried, and the organic components in the raw material solution film are removed. Removed by pyrolysis. Thereby, the dry film 130 from which the organic component having a substantially constant thickness was removed was formed. Here, the concentration of water in nitrogen gas containing moisture was set to 100 ppmv.

Here, the oxygen concentration in each divided region of the dry film 130 was measured by SIMS. As shown in FIG. 21, each divided region was formed into 35 matrix-like regions in which the dry film 130 was divided into seven equal parts in the long side direction and five equal parts in the short side direction. In FIG. 21, the long side direction of the substrate 101 is the X direction, and the short side direction of the substrate 101 is the Z direction. That is, the dry film 130 was treated as having seven divided regions arranged in each row along the X direction and five divided regions arranged in each column along the Z direction. In FIG. 21, among the dry films 130, the xth (x is an integer of 1 to 7) is arranged in the + X direction from the −X side, and the zth (z is 1 to 5) in the + Z direction from the −Z side. The divided areas arranged in (integer) are denoted by the symbol A _xz .

Here, for the dry film 130, the measurement result of the oxygen concentration in each divided region shown in FIG. 22 was obtained. Specifically, the divided regions _{A 11, A 15, A 21} , A 24, A 33, A 35, A 41, A 42, A 44, A 53, A 61, A 71, oxygen in A _74, A ₇₅ Concentrations are 11, 6.8, 8.4, 10, 7.5, 8, 6.5, 4.5, 11, 8, 6.7, 8, 10, 8.3 (× 10 ²¹ atoms, respectively). / Cm ³ ). Here, the thickness of the dry film 130 is a substantially uniform predetermined value, and the oxygen concentration in each divided region indirectly indicates the oxygen content in each divided region.

  Next, the dried coating 130 is heated at about 300 ° C. for about 15 minutes in an atmosphere of a mixed gas of Se vapor and hydrogen gas, and then heated at about 550 ° C. for about 1 hour. The light absorption layer 131 as a semiconductor layer according to the included example was formed. In addition, the density | concentration of Se vapor | steam in the mixed gas supplied toward the dry membrane | film | coat 130 was 20 ppmv.

The heat treatment for the dry film 130 was performed by the thin film manufacturing apparatus 1 according to the embodiment. In this heat treatment, as shown in FIG. 23, the flow rate of the mixed gas flowing per unit time in the space region of a predetermined size in contact with the divided region having a relatively high oxygen concentration in the dry film 130 is relatively high. The supply and exhaust of the mixed gas were adjusted so as to increase. Specifically, a plurality of gases that discharge gas from the internal space 2I by discharging the gas in the internal space 2I through the _fourth , _sixth , and _eighth gas discharge portions 7 ₄ , 7 ₆ , and 7 _8. The arrangement density in which the discharge part 7 is arrange | positioned was adjusted. Further, the mixed gas is supplied to the internal space 2I by the _first , _third , and _eighth gas supply units 6 ₁ , 6 ₃ , and 6 ₈ , so that a plurality of gas supply units 6 that supply the mixed gas to the internal space 2I are provided. The arrangement density arranged was adjusted.

<(C) Fabrication of Semiconductor Layer According to Reference Example 1>
The lower electrode layer 102 including the groove portion P1 and the dry film 130 were formed in this order on one main surface of the substrate 101 by the same process under the same conditions as the fabrication of the semiconductor layer according to the example described above.

  Next, the dried coating 130 is heated at about 300 ° C. for about 15 minutes in an atmosphere of a mixed gas of Se vapor and hydrogen gas, and then heated at about 550 ° C. for about 1 hour. A light absorption layer as a semiconductor layer according to Reference Example 1 was formed. In addition, the density | concentration of Se vapor | steam in the mixed gas supplied toward the dry membrane | film | coat 130 was 20 ppmv.

  Here, the heat processing with respect to the dry film 130 was performed by the thin film manufacturing apparatus 1 which concerns on the said one Embodiment. During the heat treatment, in the thin film manufacturing apparatus 1 shown in FIG. 23, the mixed gas is supplied to the internal space 2I by all the gas supply units 6, and the gas in the internal space 2I is supplied through all the gas discharge units 7. It was discharged. That is, regardless of the oxygen concentration in the dry film 130, the flow rate of the mixed gas flowing per unit time in each spatial region of a predetermined size in contact with each divided region was made substantially constant.

<(D) Fabrication of Semiconductor Layer According to Reference Example 2>
The lower electrode layer 102 including the groove portion P1 and the raw material solution film were formed in this order on one main surface of the substrate 101 by the same process under the same conditions as the fabrication of the semiconductor layer according to the example described above.

  Next, the raw material solution film is heated at about 300 ° C. for about 10 minutes in an atmosphere of nitrogen gas containing almost no moisture, whereby the raw material solution film is dried, The organic components of were removed by thermal decomposition. Thereby, the dry film from which the organic component whose thickness is substantially constant was removed was formed.

  Next, the dried film is heated at about 300 ° C. for about 15 minutes in a mixed gas atmosphere of Se vapor and hydrogen gas, and then heated at about 550 ° C. for about 1 hour. A light absorption layer as a semiconductor layer according to Reference Example 2 was formed. In addition, the density | concentration of Se vapor | steam in the mixed gas supplied toward the dry membrane | film | coat 130 was 20 ppmv.

  Here, the heat treatment for the dry film was performed by the thin film manufacturing apparatus 1 according to the above-described embodiment. During the heat treatment, in the thin film manufacturing apparatus 1 shown in FIG. 23, the mixed gas is supplied to the internal space 2I by all the gas supply units 6, and the gas in the internal space 2I is supplied through all the gas discharge units 7. It was discharged.

<(E) Production of photoelectric conversion device>
The buffer layer 132, the groove portion P2, and the upper electrode layer 104 are respectively formed on the light absorbing layer 131 according to the above-described embodiment, the light absorbing layer according to the reference example 1, and the light absorbing layer according to the reference example 2. The collector electrode 105 and the groove part P3 were formed in this order. Thus, the photoelectric conversion device 121 according to the example, the photoelectric conversion device according to the reference example 1, and the photoelectric conversion device according to the reference example 2 were manufactured. Each part formed here was formed by the same process as the manufacturing process of the photoelectric conversion device 121 according to the one embodiment.

  Specifically, the substrate 101 on which each light absorption layer is arranged is immersed in a solution in which cadmium acetate and thiourea are dissolved in ammonia water, so that the thickness is 50 nm on each light absorption layer. A buffer layer 132 mainly containing CdS was formed. The groove part P2 was formed by mechanical scribing using a scribe needle. Further, the transparent upper electrode layer 104 mainly containing ZnO doped with Al was formed on the buffer layer 132 by a sputtering method. Further, the collector electrode 105 was formed from a predetermined formation target position on the upper surface of the upper electrode layer 104 to the inside of the groove portion P2. The collector electrode 105 is formed, for example, by printing a metal paste in which silver metal powder is dispersed in a resin binder to have a predetermined pattern, and solidifying the printed metal paste by drying. It was. Furthermore, the groove part P3 was formed by mechanical scribing using a scribe needle. In addition, the groove part P3 was formed in the position which divides between each adjacent row | line | column in the divided area | region of 5 rows along the Z direction shown by FIG.

<(F) Measurement of photoelectric conversion efficiency in photoelectric conversion device>
The photoelectric conversion efficiency of the photoelectric conversion device 121 according to the example manufactured as described above, the photoelectric conversion device according to the reference example 1, and the photoelectric conversion device according to the reference example 2 was measured by a steady light solar simulator.

Specifically, each photoelectric conversion device was divided into 35 photoelectric conversion devices (also referred to as divided photoelectric conversion devices) by cutting so as to correspond to the 35 divided regions shown in FIG. And the wiring for output was provided in the lower electrode layer 102 and the current collection electrode 105 of each division | segmentation photoelectric conversion apparatus. In the steady light solar simulator, the photoelectric conversion efficiency was measured under the condition that the irradiation intensity of light on the light receiving surface of the split photoelectric conversion device was 100 mW / cm ² and the air mass (AM) was 1.5. In addition, photoelectric conversion efficiency shows the ratio by which the energy of sunlight is converted into electrical energy in a divided photoelectric conversion apparatus. Here, the value of the electrical energy output from the split photoelectric conversion device is divided by the value of the energy of sunlight incident on the split photoelectric conversion device, and multiplied by 100, whereby the photoelectric conversion efficiency is derived. .

<(G) Measurement result of photoelectric conversion efficiency in photoelectric conversion device>
FIG. 24 is a diagram illustrating an in-plane distribution of photoelectric conversion efficiency in the photoelectric conversion device 121 according to the example. Of the photoelectric conversion device 121 according to the embodiment, the divided regions A ₁₁ , A ₁₅ , A ₂₄ , A ₃₁ , A ₃₂ , A ₃₅ , A ₄₃ , A ₅₁ , A ₅₄ , A ₆₂ , A _{71 shown in FIG.} , A ₇₄ , and A ₇₅ , the photoelectric conversion efficiencies of the divided photoelectric conversion devices are 13.5%, 12.9%, 11.8%, 13.6%, 13.4%, and 13.2%, respectively. 12.6%, 12.7%, 11.9%, 13.0%, 12.6%, 12.5%, 13.8%. And the average value of photoelectric conversion efficiency was 12.9%, and the standard deviation (sigma) which shows the dispersion | variation in photoelectric conversion efficiency was 0.62.

FIG. 25 is a diagram illustrating an in-plane distribution of photoelectric conversion efficiency in the photoelectric conversion device according to Reference Example 1. Among the photoelectric conversion devices according to Reference Example 1, the divided regions A ₁₁ , A ₁₅ , A ₂₄ , A ₃₁ , A ₃₂ , A ₃₅ , A ₄₃ , A ₅₁ , A ₅₄ , A ₆₂ , A _{65 shown in FIG.} , A ₇₁ , A ₇₄ , and A ₇₅ respectively have photoelectric conversion efficiencies of 11.8%, 12.9%, 11.9%, 12.5%, 13.6%, and 11 respectively. 4%, 12.1%, 13.1%, 11.9%, 10.5%, 11.3%, 12.6%, 10.9%, 12.0%. And the average value of photoelectric conversion efficiency was 12%, and the standard deviation (sigma) which shows the dispersion | variation in photoelectric conversion efficiency was 0.86.

FIG. 26 is a diagram illustrating an in-plane distribution of photoelectric conversion efficiency in the photoelectric conversion device according to Reference Example 2. Among the photoelectric conversion devices according to Reference Example 2, the divided regions A ₁₁ , A ₁₅ , A ₂₄ , A ₃₂ , A ₃₅ , A ₄₃ , A ₅₁ , A ₅₄ , A ₆₂ , A ₇₁ , A _{74 shown in FIG.} , A ₇₅ respectively, the photoelectric conversion efficiencies in the divided photoelectric conversion devices are 10.7%, 12.1%, 11.6%, 10.6%, 11.7%, 12.4%, 11. They were 3%, 11.5%, 11.1%, 10.5%, 11.8%, and 8.3%. And the average value of photoelectric conversion efficiency was 11.5%, and the standard deviation (sigma) which shows the dispersion | variation in photoelectric conversion efficiency was 0.62.

  As shown in FIGS. 24 to 26, the atmosphere when the raw material solution film is pyrolyzed contains more water than the atmosphere when the raw material solution film is pyrolyzed. It has been found that the photoelectric conversion efficiency in the photoelectric conversion device is increased when it is. And, during the heat treatment for the dry film, the variation in the photoelectric conversion efficiency in the photoelectric conversion device is reduced by changing the supply amount of the chalcogen element per unit time according to the in-plane distribution of the oxygen content of the dry film. It has been found that the photoelectric conversion efficiency is further increased. In the light absorption layer 131 according to the example, it was estimated that the CIGS layer close to the ideal composition was uniformly formed.

1 thin-film deposition apparatus 2 furnace 2I inner space 4,4A cassette 4R substrate placement region _{5,5 m, 5 1 ~5 7,} 5A, 5A n, 5A 1 ~5A 8 the heated substrate 6,6 _n, 6 ₁ ~ 6 ₈ gas supply unit 7, 7 _n , 7 _{1 to} 7 ₈ gas discharge unit 8 heater 101 substrate 102 lower electrode layer 103 photoelectric conversion layer 104 upper electrode layer 105 current collecting electrode 110 photoelectric conversion cell 121 photoelectric conversion device 130 dry film 131 light absorbing layer 132 buffer layer _{A xz, A 11 ~A 15,} A 21 ~A 25, A 31 ~A 35, A 41 ~A 45, A 51 ~A 55, A 61 ~A 65, A 71 ~A 75 divided area C1 controller _{E7, E7 n, E7 1 ~E7} 8 gas exhaust adjusting unit P1, P2, P3 groove _{S6, S6 n, S6 1 ~S6} 8 gas source

Claims (15)

A thin film manufacturing method for manufacturing a compound semiconductor thin film containing a chalcogen element,
(A) preparing one or more substrates on which a first film containing at least a metal element other than the chalcogen element contained in the compound semiconductor is disposed;
(B) Heating the one or more substrates in an atmosphere containing at least one of moisture and oxygen to cause partial oxidation of the metal element, thereby providing one main surface of the one or more substrates Forming a second film containing the metal element partially oxidized thereon;
(C) Arranging the one or more substrates in which the second coating is disposed on one main surface in a substrate arrangement region in one heating furnace;
(D) adjusting at least one of supply of the gas containing the chalcogen element into the one heating furnace by a plurality of gas supply units and exhaust from the one heating furnace by a plurality of gas discharge units Accordingly, the supply amount of the chalcogen element per unit time differs according to the distribution of oxygen content for each second coating in each space region of a predetermined size in contact with each second coating. Forming a thin film of the compound semiconductor on the one or more substrates by heating the one or more substrates while flowing a gas containing a chalcogen element. (E) A substrate different from the one or more substrates on which a third film containing at least a metal element other than the chalcogen element contained in the compound semiconductor is disposed is at least one of moisture and oxygen. By heating in an atmosphere that includes the metal element, a part of the metal element is oxidized to form a fourth film containing the metal element that is partly oxidized on one main surface of the another substrate. Process,
(F) Based on the measurement result of the fourth coating disposed on the other substrate, the distribution of the oxygen content for each of the second coatings disposed on the one or more substrates. The thin film manufacturing method according to claim 1, further comprising a step of obtaining.   The thin film manufacturing method of Claim 2 which performs the said process (e) and the said process (f) for every combination of the specification of the apparatus used in the said process (a) and the said process (b).   The thin film manufacturing method of Claim 2 or Claim 3 which performs the said process (e) and the said process (f) for every combination of the apparatus used in the said process (a) and the said process (b).   The thin film manufacturing method according to any one of claims 2 to 4, wherein the step (e) and the step (f) are performed for each specification of the first film used in the step (b). . A thin film manufacturing method for manufacturing a compound semiconductor thin film containing a chalcogen element,
(A) preparing two or more substrates on which a first film containing at least a metal element other than the chalcogen element contained in the compound semiconductor is disposed;
(B) Heating the two or more substrates in an atmosphere containing at least one of moisture and oxygen causes a part of the metal element to be oxidized, and one main surface of the two or more substrates Forming a second film containing the metal element partially oxidized thereon;
(C) Arranging the two or more substrates in which the second film is disposed on one main surface in a substrate arrangement region in one heating furnace;
(D) adjusting at least one of supply of the gas containing the chalcogen element into the one heating furnace by a plurality of gas supply units and exhaust from the inside of the one heating furnace by a plurality of gas discharge units Accordingly, the chalcogen element is provided in a space region of a predetermined size in contact with each second coating so that the supply amount of the chalcogen element per unit time varies depending on the oxygen content of each second coating. Forming a thin film of the compound semiconductor on the two or more substrates by heating the two or more substrates while flowing a gas containing the thin film. (E) Another substrate different from the two or more substrates on which a third film containing at least a metal element other than the chalcogen element contained in the compound semiconductor is disposed is formed by using at least one of moisture and oxygen. By heating in an atmosphere that includes the metal element, a part of the metal element is oxidized to form a fourth film containing the metal element that is partly oxidized on one main surface of the other substrate. Process,
(F) The step of obtaining the oxygen content for each of the second coatings disposed on the two or more substrates based on the measurement result of the fourth coating disposed on the other substrate. The thin film manufacturing method according to claim 6, further comprising:   The thin film manufacturing method of Claim 7 which performs the said process (E) and the said process (F) for every combination of the specification of the apparatus used in the said process (A) and the said process (B).   The thin film manufacturing method of Claim 7 or Claim 8 which performs the said process (E) and the said process (F) for every combination of the apparatus used in the said process (A) and the said process (B).   The thin film manufacturing method according to any one of claims 7 to 9, wherein the step (E) and the step (F) are performed for each specification of the first film used in the step (B). .   The chalcogen element contained in the gas flowing per unit time in each space region according to the amount of gas supplied per unit time into the one heating furnace by each gas supply unit of the plurality of gas supply units The method for producing a thin film according to any one of claims 1 to 10, wherein the supply amount is adjusted.   The chalcogen element contained in the gas flowing per unit time in each space region by the amount of gas discharged per unit time from the inside of the one heating furnace by each of the gas discharge units of the plurality of gas discharge units The method for producing a thin film according to any one of claims 1 to 11, wherein the supply amount is adjusted.   The chalcogen contained in the gas flowing per unit time in each space region according to the concentration of the chalcogen element in the gas supplied into the one heating furnace by each gas supply unit of the plurality of gas supply units The thin film manufacturing method according to any one of claims 1 to 12, wherein the supply amount of the element is adjusted.   14. The supply amount of the chalcogen element contained in the gas flowing per unit time in each space region is adjusted according to the arrangement density of the plurality of gas supply units. The thin film manufacturing method as described in any one of.   15. The supply amount of the chalcogen element contained in the gas flowing per unit time in each space region is adjusted according to the arrangement density of the plurality of gas discharge units. The thin film manufacturing method as described in any one of.

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