JP4177480B2 - Compound semiconductor film and related electronic device manufacturing method - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
This invention was made with the support of the US Government under contract number DE-FG03-96ER82191 / A000 of the Department of Energy. The United States government has certain rights in this invention.
The present invention relates to a method of manufacturing a structure including ternary and higher order compound semiconductors, such a structure, and an electronic device including such a structure.
[0002]
[Prior art]
Photoelectric conversion engineering relates to the direct conversion of light or solar energy into electricity through the use of active electronic devices called solar cells. Solar cells are generally fabricated on polycrystalline or single crystal silicon wafers. However, the cost of electricity generated using silicon-based solar cells is somewhat higher than that available from a typical power system grid. The manufacturing cost of photovoltaic products is standard 100mW / cm²Often expressed in dollars per watt generated under illumination.
In order to obtain thin film solar cell technology that can compete with common silicon-based photovoltaic products and conventional power generation methods, using a cost effective method with high throughput and high rate utilization of materials, Film growth techniques must be developed that can deposit solar cell grade, electronic active layer of absorber material and other elements of the solar cell on the substrate. Therefore, there has been a continuous effort to develop an inexpensive solar cell based on a thin polycrystalline compound semiconductor absorber layer.
[0003]
IB-IIIA-VIA group materials are promising as absorber layers for high-efficiency solar cells. In fact, relatively efficient thin film devices are Cu (In, Ga) Se grown by vacuum deposition techniques.₂Already manufactured on absorber film. A demonstrated conversion efficiency of more than 17% confirms that this material has the ability to produce fairly efficient active devices when used in thin film solar cell structures.
The electrical and optical properties of IB-IIIA-VIA compound films depend on their chemical composition, chemical and structural defects, which in turn are related to film growth techniques and parameters. There are a variety of deposition techniques used for the growth of IB-IIIA-VIA compound semiconductor films. However, it is important to obtain a material with sufficient optoelectronic and structural properties necessary for the manufacture of active electronic devices such as solar cells.
[0004]
In solar cells based on Group IB-IIIA-VIA absorber films, a significant amount of two phases, such as Group IIIA-VIA compounds and in particular Group IB-VIA compounds in the absorber film, is responsible for the electronic properties of the compound and hence Generally, the characteristics of the solar cell are deteriorated. Further, it would be desirable to have an absorber material having cylindrical particles equal to a diameter of at least about 0.5 μm in a thin film solar cell structure. In addition, for commercial competitiveness, this technology uses low-cost equipment and processes to compose a layer that is relatively uniform on a very large substrate, such as an area unit of several square feet. Should be able to adhere.
An important composition parameter for IB-IIIA-VIA thin films is the molecular ratio of group IB elements to group IIIA elements. This is generally called the I / III ratio. In general, the acceptable range of I / III molar ratio for Cu-containing solar cells using IB-IIIA-VIA group materials is about 0.80-1.0, but exogenous with dopants such as Na This ratio can be as low as about 0.6 if doping is required. If the I / III ratio exceeds 1.0, the low resistivity copper selenide phase generally precipitates and degrades the performance of the device.
[0005]
One technique that has resulted in relatively good quality IB-IIIA-VIA films for the manufacture of solar cells is the co-deposition of group IB, group IIIA and group VIA elements on a heated substrate. Bloss et al.'S paper in the review magazine (“Thin Film Solar Cell”,Advances in photoelectric conversion engineering, Vol. 3, pages 3-24, 1995), the film growth of this technology takes place in a high vacuum chamber, and the deposition ratio of group IB elements to group IIIA elements is Carefully controlled to keep the I / III ratio within an acceptable range.
However, uniform deposition by vapor deposition is difficult mainly on large-area substrates, and because the vacuum apparatus is high, the vapor deposition method is easily accepted for producing large-area films at low cost. Can not. Co-sputtering of group IB elements and group IIIA elements such as Cu in the presence of group VIA vapors such as Se has also been investigated as a possible method of compound film growth. However, this technique has the disadvantage of the most likely yield problem due to insufficient performance to control the I / III ratio.
[0006]
Another technique for growing IB-IIIA-VIA compound thin films for solar cells is that at least two elements of the IB-IIIA-VIA group material are first deposited on the substrate, and then to each other and / or It is a two-step process that is reacted in a reaction atmosphere by a high-temperature annealing process. Vijay K. Kapur et al., 1986, U.S. Pat.No. 4,581,108, James H. Ermer et al., 1989, U.S. Pat.No. 4,798,660, and Burent U.S. Pat.No. 5,028,274 issued in 1991 to Bulent M. Basol et al. Describes electrodeposition of group IB and IIIA elements on a substrate followed by selenization or sulfidation followed by selenization. Teaches direct current magnetron sputtering of Cu and In layers on a substrate to be deposited, and deposition of group IB and group IIIA elements on a substrate pre-coated with a thin Te film followed by selenization or sulfidation, respectively. ing.
In a two-step process, large area magnetron sputtering techniques can be used to deposit separate layers containing Group IB and Group IIIA elements to create a precursor film. CuInSe₂In the case of growth, for example, Cu and In layers are sputter deposited on an unheated substrate, and then the composite film is heated at high temperatures as shown in US Pat. No. 4,798,660 and US Pat. No. 5,028,274.₂Selenization can be performed with Se gas or Se vapor.
[0007]
Film growth techniques require tight control of the material composition during the deposition process for the typical purpose that the total I / III ratio should be within an acceptable range of about 0.80 to 1.0 in the final film. For mass production of photovoltaic modules, this ratio should be uniform across large area substrates. In the two-step process, the uniformity and thickness of each layer must be controlled.
If the I / III ratio is greater than 1.0, Cu selenide phase separation occurs in the IB-IIIA-VIA group compound layer. Layers containing Cu selenide phase have a low resistivity and are generally not used in active device manufacturing. However, these high Cu films have excellent structural properties and large particle sizes. The relationship between the structural properties of IB-IIIA-VIA materials and their composition is beneficial, especially in the co-evaporation method, to improve the structural properties of the grown film during I / III during film growth processing. It can be used by intentionally increasing the ratio to 1.0 or higher and then decreasing the I / III ratio back to an acceptable range by the time the deposition process is finished. Films grown in this manner often have large particle sizes and satisfactory electronic properties. Therefore, it is generally acceptable to change the I / III ratio during the deposition and growth of IB-IIIA-VIA compounds, but in this case the total ratio of the final film is within the range of 0.80 to 1.0. To be.
Since uniformity and control of the I / III ratio in the material is important for compounds in the IB-IIIA-VIA group, an attempt was made to fix this ratio of the material prior to the deposition process, and then the fixed composition Is transferred to a thin film formed using this material. CuInSe by this method₂Early attempts to grow were made with CuInSe previously produced as a deposition source or sputtering target.₂It was by vapor deposition and sputtering using compound materials. However, these efforts do not provide repetitive compositional control (this can be achieved with Se and / or In in a vacuum environment).₂Does not result in solar cell grade material (which may result from loss of Se). In the case of sputtering, a problem arises by changing the characteristics of the target surface. A relatively efficient solar cell is CuInSe.₂Recently demonstrated on layer obtained by laser ablation of target (performed in 1993 by H. Dittrich et al.First twenty three Times IEEE of PV Expert meetingHowever, this method is not practical for large-scale production.
[0008]
Other attempts to make IB-IIIA-VIA group compound films using materials having a pre-fixed composition included screen printing layers on substrates and their conversion to compounds. Ti Arita et al. Published their 1988 publication (1988First 20 Times IEEE of PV Expert meeting(Page 1650 of the minutes) showed screen printing technology including: That is, pure Cu, In and Se powders are mixed in a 1: 1: 2 composition ratio to form an initial material, and these powders are crushed with a ball mill to produce a paste that can be screen printed, This paste is screen printed onto the substrate and the precursor film is sintered to form a compound layer. This grinding was performed in water or a medium such as ethylene glycol monophenyl ether to reduce the particle size and the paste was produced using a propylene glycol binder. The paste material was deposited on a high temperature borosilicate glass substrate by a screen printing method to form a film. The post-deposition processing step consisted of annealing the film in nitrogen gas at 700 ° C. to form a compound film on the substrate.
In order to evaluate the photovoltaic properties of the resulting compound, a thick pellet was made from the material obtained as a result of the grinding and sintering steps, and a solar cell was fabricated on this pellet. For these devices, the efficiency was reported to be only about 1%. In addition, researchers are interested in CdS / CuInSe₂CuInSe in which a thin film junction was sintered by high frequency sputtering₂Although it was reported that it was also produced by depositing a CdS film on the film, the researchers concluded that it was not possible to obtain photovoltaic characteristics better than the photovoltaic characteristics of the pellet sample. Their reported data show that In powder is oxidized during the grinding process, Cu, In and Se react with each other during the grinding process, and CuInSe obtained after the sintering process.₂The material showed a specific resistance of about 1.0 ohm · cm. This resistivity is typical of CuInSe resulting in efficient solar cells.₂The value is only about 0.01 to 1% for, which may indicate the presence of harmful Cu-Se phases. Furthermore, the sintering temperature of 700 ° C. is very high for an inexpensive solar cell structure using a soda lime glass substrate.
[0009]
CuInSe deposited by screen printing method₂A thin layer of was also reported by a research group at the University of Ghent in Belgium. A. Vervaet et al., A 1989 publication referencing the work of Ti Arita et al. (1989Of the 9th European Community PV Solar energy conferencePage 480), the indium powder is easily oxidized and the final film is In (OH)_ThreeOr In₂O_ThreeTo produce an unfavorable phase such as Therefore, Gent University research group technology is CuInSe₂CuInSe as initial material by crushing ingot₂Forming a powder; and CuInSe₂Grinding the powder in a ball mill and adding extra Se powder and other chemicals such as 1,2-propanediol to prepare a screen-printable paste, borosilicate substrate and alumina The steps of screen printing the layer onto the substrate and performing high temperature sintering (500 ° C. or higher) of the layer to form a compound film were used. The difficulty of this method is CuInSe₂It was to obtain a suitable sintering agent or flux for film formation. Of the many agents studied, copper selenide is the best for grain growth, but films containing this phase have an I / III ratio greater than 1.0, which is useful for active device manufacturing. Could not be used.
[0010]
More recently, a group at the University of Ghent has identified a relatively low (about 400 ° C.) melting point compound, CuTlSe, as a fluxing agent.₂Experimented with. M. Casteleyn et al. Published their 1994 publication (1994First 12 Times of europe PV Solar energy conferencePp. 604) of CuInSe₂CuTlSe with the formulation of₂Was used to demonstrate film growth for films at an acceptable I / III ratio. However, the solar cell fabricated on the resulting layer was still functional and had a conversion efficiency of only about 1%. The sintering temperature of 600 ° C. or higher used in this process was high even for an inexpensive glass substrate. CuInSe as initial material₂The use of a does not give good results because there is not enough sintering agent that will not have a detrimental effect on the electronic properties of the final film obtained by this technique. The sintering temperature used in the screen printing technique referred to above is very high (> 600 ° C.) for the use of inexpensive substrates for the deposition of IB-IIIA-VIA group compound films.
In addition to the obstacles associated with controlling the macroscale uniformity of the I / III ratio across a large area substrate, there are also problems associated with microscale non-uniformity of IB-IIIA-VIA group compound thin films. In U.S. Pat.No. 5,445,847 issued in 1995 to Ti Wada et al., The investigator found that a layer of group IB elements and a layer of group IIIA elements in the presence of chalcogen to obtain a chalcopyrite type compound. Treated with heat. The researchers observed deviations in the composition ratio of group IB elements to group IIIA elements in the resulting compound, and showed that the composition itself was not always very constant. As a countermeasure to this problem, researchers used an IB-IIIA group oxide composition having a high melting temperature instead of the elemental layer. Researchers say that the oxide composition of the IB-IIIA group does not dissolve based on the heat treatment temperature in a reducing atmosphere containing a VIA group element or a reduced compound of the VIA group element, and the initial composition is maintained on a microscale I concluded that I could do it. X-ray diffraction data showed the phase structure of the IB-IIIA-VIA group. Clearly, however, no data was published regarding the electronic quality of these phases, and no active devices such as solar cells were produced.
[0011]
Another scheme for microscale control of the I / III ratio is shown in Ti Wada et al. European Patent No. 91316575.7 (1994 Publication No. 0595115A1). Thus, chalcopyrite type compounds contain elements of the VIA group that contain Cu, In and In compounds or compounds containing both In and Cu selected from the group consisting of oxides, sulfides and selenides. It is treated by annealing in an atmosphere. Cu / In ratio less than about 1.0 is solar cell grade CuInSe₂As desired for compound films, the extra group VIA element In must be present prior to annealing. According to these researchers, In produces minute non-uniformities in the layer due to its low melting point. The idea was therefore to replace In with its high melting point oxide, sulfide or selenide. This was accomplished by the reaction to deposit multiple layers on the substrate and form the desired compound, just as in a two-step process. Some examples of multilayer deposition include electron beam evaporation or sputtering of Cu and In layers followed by sputtering or laser ablation of indium oxide, indium sulfide or indium selenide, and In oxides, sulfides or selenides. Cu followed by film adhesion₁₁In₉Including co-deposition of alloy layers and deposition of indium oxide and also copper oxide layers, or indium selenide and copper selenide layers, or Cu and In layers followed by deposition of indium sulfide and copper indium sulfide layers. Yes.
[0012]
Processing techniques that use multiple layers of attachment materials containing elements from groups IB and IIIA can handle microscale compositional uniformity issues by including high melting point compounds in the layer, however, more than just As in a simple two-step process, it is not expected to deal with the more important issue of macroscale uniformity of the I / III ratio. In other words, if multiple layers containing IB and IIIA elements need to be deposited on a large area substrate, the thickness and thickness uniformity of each layer containing IB and IIIA elements is strict. Control is needed. In this regard, for example, Cu / In / In₂O_ThreeOr Cu / In / Cu₂In₂O_FiveThe compositional control for the stack is more complicated than for example for a simple two-step Cu / In stack.
[0013]
[Problems to be solved by the invention]
As the above discussion of the prior art demonstrates, there is a need for a technique that produces IB-IIIA-VIA group (and related) compound films on large area substrates with good compositional uniformity. There is also a need for such compound films with excellent electronic properties to produce such compound films suitable for the production of active electronic devices such as solar cells.
[0014]
[Means for Solving the Problems]
  According to the present invention, in a method for producing a compound film,
  (A) supplying a starting material comprising a powdery substance having a group IB element and a group IIIA element;
  (B) a raw material comprising IB-IIIA group alloy-containing particles having at least one IB-IIIA group alloy phase from the starting material, wherein the IB-IIIA group comprises an IB group element in the raw material and Preparing more than 50 mol% of each of the group IIIA elements;
  (C) depositing said source material on a base in the form of a precursor film;
  (D) The precursor film is heated in a heat treatment atmosphere corresponding to the composition of the constituent material to produce a film containing a IB-IIIA-VIA group compound, thereby producing a compound film. A method is provided.
  The ratio of moles of group IB elements / group IIIA elements in the source material is greater than 0.80 and less than 1.0, or substantially less than 1.0 in the source material. Again, this ratio can be substantially greater than 0.8 and less than 1.0 in the compound film.
  The IB-IIIA alloy is preferably more than 60 mol%, particularly 90 mol%, and more than 60 mol%, particularly 90 mol% of the group IIIA element, of the IB group element of the raw material. .
  The IB-IIIA alloy-containing particles preferably include at least one group IB or IIIA element phase.
  Moreover, it is preferable that the raw material further contains a VIA group-containing particle.
  Furthermore, it is preferable that the step of supplying the starting material includes generation of a powder composed of the IB-IIIA alloy-containing particles.
  In particular, it is preferable that the powder aggregate of the raw material in the preparation step subsequent to the supplying step is substantially composed of particles smaller than 20 microns in particle size, and particularly composed of particles substantially smaller than 2 microns.
  The precursor film may be a single layer, and the compound film may be thicker than 0.5 microns and thinner than 20 microns, especially thicker than 1 micron and thinner than 10 microns. preferable.
  In the method of the present invention, the step of supplying the starting material comprises a step of supplying a powder of the IB-IIIA alloy-containing particles, and the preparing step comprises an IB-IIIA group alloy from the starting material. Preferably, the method includes a step of generating ink containing the contained particles.
  The IB-IIIA alloy-containing particles preferably include a group IIIA material selected from group IB Cu, and In or Ga. In particular, the chemical formula InxGa (1-X) (where X is It is preferable to include a group IIIA material made of an alloy of In and Ga, which is expressed by an expression greater than 0 and less than 1.
  Furthermore, the IB-IIIA group alloy-containing particles are preferably dispersed throughout the raw material.
  The alloy phase may contain a dopant, and the dopant is preferably an element selected from Na, K and Li.
  The dopant may be contained in the raw material or at the stage of the compound film.
  According to the present invention, there is also a method for manufacturing an electronic device comprising:
  (A) supplying a starting material comprising a powdery substance having a group IB element and a group IIIA element;
  (B) a raw material comprising IB-IIIA group alloy-containing particles having at least one IB-IIIA group alloy phase from the starting material, wherein the IB-IIIA group comprises an IB group element in the raw material and Preparing more than 50 mol% of each of the group IIIA elements;
  (C) depositing said source material on a base in the form of a precursor film;
  (D) An electronic device comprising the step of heating the precursor film in a heat treatment atmosphere corresponding to the constituent material composition to produce a film containing a compound of the IB-IIIA-VIA group is manufactured. A method is provided.
  In the method, the step of supplying the starting material comprises the step of supplying a powder of the IB-IIIA group alloy-containing particles, and the preparing step includes an ink containing IB-IIIA group alloy-containing particles from the starting material. Preferably, the method comprises a step of generating
  Moreover, it is preferable that the powder aggregate of the raw material in the preparation step following the supply step is substantially composed of particles having a particle size of less than 20 microns.
  Furthermore, it is preferable that the raw material powder aggregate in the preparation step is substantially composed of particles having a particle diameter of less than 2 microns.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
The foregoing and additional features and advantages of the present invention will become more apparent from the detailed description that follows and the accompanying drawings. In the drawings and written description, numerals indicate various functions of the invention in all parts relative to the drawings and written description, and like numerals indicate like functions.
[0016]
A typical general structure of a conventional solar cell of a group IB-IIIA-VIA compound as well as this structure produced according to the present invention is shown in FIG. The device is fabricated on a substrate that includes a sublayer 10 such as a glass material. The p-type absorber film 12 is attached over the conductive layer 11 made of, for example, molybdenum (Mo). This conductive layer serves as the back resistive contact of the solar cell and is a coating on the sublayer of the substrate. Both the sublayer 10 and its coating 11 can be regarded as a substrate.
An n-type transparent window layer 13 is formed on the p-type absorber film 12 through which radiation enters the device. The solar cell is completed by depositing a metal grid finger pattern 14 over the window layer 13 if necessary. The most commonly used p-type absorber film 12 is CuIn_1-xGa_xSe_{2 (1-y)}S_2yIB-IIIA-VIA absorber film 12 having a composition that can be represented by the general chemical formula: 0 ≦ x ≦ 1 and 0 ≦ y ≦ 1. This group of compounds is Cu (In, Ga) (Se, S)₂It is also shown by the general chemical formula
[0017]
The constituent elements of the representative specific compounds described in this document are shown in the CRC Chemical & Physics Handbook (72nd edition) published by CRC Press, 1991-1992, for example on the inner cover table. Grouped according to the notation of the columns of the periodic table defined by the Chemical Abstract Service (CAS).
Various materials deposited by various methods can be used to provide the components of the apparatus shown in FIG. For example, the sublayer 10 of the substrate may be rigid or flexible, may be conductive, or may be insulating. Possible materials for the sublayer 10 are insulating sublayer sheets or flexible foils such as glass, alumina, mica or polyimide materials or Mo, tungsten (W), tantalum (Ta), titanium (Ti), aluminum ( Including, but not limited to, conductive materials such as Al), nickel (Ni) and stainless steel.
[0018]
Conductive layer or coating 11 is good for preferred materials Mo, W, Ta, Ti, gold (Au), and IB-IIIA-VIA group semiconductor absorber film 12 such as nitride, phosphide or telluride Made of conductive material that provides a reliable resistive contact. The conductive layer 11 may actually consist of two or more material layers. If the sublayer 10 is a conductive material that provides a good resistive contact to the semiconductor absorber film 12, the conductive layer 11 is not necessary.
[0019]
The materials of the IB-IIIA-VIA group semiconductor absorber film 12 that can be deposited using the teachings of the present invention are copper (Cu), silver (Ag), aluminum (Al), gallium (Ga), indium (In), Selected from the group consisting of ternary or higher order selenides, sulfides, tellurides of thallium (Tl) and its alloys. The preferred material for the layer of absorber film 12 is CuIn_1-xGa_xSe_{2 (1-y)}S_2yWhere 0 ≦ x ≦ 1 and 0 ≦ y ≦ 1. This layer contains dopants such as potassium (K), sodium (Na), lithium (Li), phosphorus (P), arsenic (As), antimony (Sb) and bismuth (Bi) to enhance its electronic properties. Further, it may be included.
The window layer 13 is made of, for example, a compound of cadmium (Cd) such as Cd (Zn) S and ZnSe, zinc (Zn) and sulfur (S) or selenium (Se), ZnO, indium tin oxide, tin oxide, and the like. Similar to transparent conductive oxides, it has one or more layers of transparent semiconductor material commonly used in solar cells. Different layers can be paired to optimize device performance. Possible structures for optimized window materials are Cd (Zn) S / TCO, ZnSe / TCO, In (Ga) -selenide / TCO, In (Ga) -sulfide / TCO, and In (Ga). -Including but not limited to oxide / TCO, where TCO refers to one or more layers of transparent conductive oxides such as ZnO, indium tin oxide, and tin oxide. The material of the window layer 13 can be deposited by various techniques well known in the art. As is conventionally understood, notations such as “Cd (Zn) S” and “In (Ga)” are used for all compositions from pure CdS to pure ZnS and for all compositions from pure In to pure GaS. Means composition.
A finger pattern 14 can be deposited on the device structure to reduce the series resistance introduced by the window layer 13. In modular structures that use narrow solar cells, there is no need for finger patterns 14. An anti-reflective coating (not shown) can also be applied over the window layer 13, further improving the efficiency of the finished solar cell.
The preferred electrical type of the IB-IIIA-VIA absorber film 12 in FIG. 1 is p-type, and the preferred type of the window layer 13 is n-type. However, n-type absorbers and p-type window layers may also be used. The preferred device structure of FIG. 1 is commonly referred to as a “substrate type structure”. The “upper layer type” structure first deposits a window layer on a transparent sheet substrate, such as a substrate made of glass material, then deposits an IB-IIIA-VIA compound absorber film and finally conductive. It can also be constructed by forming the back resistive contact of the device with layers. In this upper layer structure, solar energy or light enters the device from the upper layer side facing the solar energy or light.
[0020]
FIG. 2 shows the general process of treatment 21 for the deposition of the IB-IIIA-VIA compound film 27, where the I / III ratio is fixed with the source material 23 prior to film deposition. The fixed composition is transferred to the precursor film 25 and used to form the compound film 27 of the IB-IIIA-VIA group. The starting material 20 is the initial material used in the pre-deposition processing step 22, where the starting material 20 is processed to be suitable for deposition on a selected substrate in the form of a precursor film 25. The product of the deposition pretreatment step 22 is a source material that can be transferred onto the substrate in the form of a precursor film 25 by the film deposition step 24. In the post-deposition processing step 26 of the precursor film 25, a final IB-IIIA-VIA group compound film 27 is formed.
With reference to FIG. 2, the preferred form of the starting material 20 of the present invention is a powder. The composition of this powder is shown schematically in FIG. In FIG. 3, the starting material 20 includes an IB-IIIA group alloy-containing particle 31, a group IB element particle 32, a group IIIA element particle 33, and a group VIA element particle 34. The group IB-IIIA alloy-containing particles 31 may contain a group IIIA element phase such as In and / or Ga in addition to the group IB-IIIA alloy phase. The alloy phase of the IB-IIIA group that may be included in the particles 31 is Cu._FourIn, Cu₂In, Cu₁₁In₉, Cu₁₆In₉, CuIn₂, Cu₉In_Four, Cu₇In_Three, CuIn, Cu₇In_Four, CuGa₂, Cu₉Ga_FourAnd alloys thereof, but not limited thereto. The exact phase content of the particles 31 depends on the formulation method and the targeted I / III ratio. For example, particles 31 obtained by techniques involving rapid cooling of dissolved IB-IIIA compositions are likely to contain an IB-IIIA alloy phase that exists at high temperatures. If such a powder is later annealed at low temperatures, its content may change and become more stable at lower temperatures. Even more generally, group IB and / or group IIIA element particles 32 and 33 may not be present.
It is important that the I / III ratio of the IB-IIIA alloy-containing particles 31 is constant and known in advance, and that the overall I / III ratio of the starting material 20 powder is constant and known. is there. For example, if the group IB element is Cu, the group IIIA element is In, and the starting material 20 is a mixture of Cu-In alloy-containing powder, Cu powder and In powder, Cu₃₁/ (Cu₃₁+ Cu₃₂)> 0.9 and In₃₁/ (In₃₁+ In₃₃)> 0.9, preferably Cu₃₁Is the content of Cu-In alloy-containing particles 31 per mole of Cu, Cu₃₂Is the Cu content per mole of Cu particles 32, and In₃₁Is the content of Cu-In alloy-containing particles 31 per mole of In, and In₃₃Is the In content of the particles 33.
[0021]
With respect to FIG. 3, the preferred Group IB element is Cu, and the preferred Group IIIA elements are In and Ga. A preferred Group VIA element is at least one selected from the group of Se, S and Te. The particles 31, 32, 33 and 34 may be irregular in shape or circular. The powder can be obtained by various methods known to those skilled in the art of powder metallurgy. These techniques include, but are not limited to, mechanical grinding of bulk materials, atomization or spinning of melts, wet metallurgy techniques, electric field techniques, deposition methods and spray pyrolysis. Recently developed spark erosion schemes and chemical techniques used for nanoparticle production are also applicable to the powder formulation used in the present invention.
[0022]
4 to 9 schematically show the process according to the invention and FIG. FIG. 4 schematically shows a Group VIA particle 34 in powder form mixed with other particles of FIG. 3 to form the starting material of FIG. 3 shown at 20 in FIG. IB-IIIA group alloy-containing particles 31 are included.
FIG. 5 shows the removal of particles larger than a predetermined size from the mixed powder of FIG. This removal is illustrated schematically by passing the starting material through screen 36. Also, this removal is a pre-adhesion process shown at 22 in FIG.
FIG. 6 schematically illustrates a powder having only smaller particles that are mixed with a liquid as a process of forming an ink. This is illustrated schematically by pouring liquid 38 from flask 40 into beaker 40 containing powder. This is part of the pre-deposition treatment shown at 22 in FIG.
FIG. 7 schematically illustrates a powder-containing liquid that is undergoing grinding for ink production. This is also part of the deposition pretreatment shown at 22 in FIG. 2 to reduce the particle size even above the level in the starting material 20. For rough purposes only, it includes a spherical portion 44 that can be lowered and rotated into the ink in the beaker 40, so that it is obtained by a grinding structure 42 that shatters the powder particles in the ink. Is shown as In fact, a typical ball mill procedure uses a ceramic mill jar filled with ground ceramic balls. When the jar is rotated or vibrated, the ball vibrates and crushes the powder in the liquid medium, forming an ink with small particles.
FIG. 8 schematically shows the crushed ink being deposited on the large substrate 46. This, of course, shows the film deposition shown at 24 in FIG. 2 on the substrate, resulting in the precursor film shown at 25 in FIG.
FIG. 9 shows a precursor on a substrate exposed to an atmosphere (in the form of a vapor) containing a Group VIA element with the application of heat to produce a Group IB-IIIA-VIA compound film on the substrate. A substrate with a material film is schematically shown, and such a compound film is shown at 27 in FIG.
[0023]
Referring back to FIGS. 2 and 7, the adhesion pretreatment step 22 as described involves grinding. Milling can be done in a liquid medium such as water, alcohol and other organic liquids or can be done by drying. The grinding can be performed at room temperature or at a low temperature. The purpose of the grinding process is to reduce the size of the particles in the raw material. This is important for the macroscale uniformity of the film being grown. The size of the particles should generally be less than the thickness of the film being grown, and most commonly should be less than or equal to 2.0 μm. This can be determined by standard techniques, such as conventional light scattering analysis, used to ensure that almost all of the particles in the group are smaller than or equal to a predetermined size. . It is also shown that such techniques are preferred to show that less than 1% of the particles exceed this size, but less than 5% are acceptable. This size can generally be regarded as the longest straight line that can be drawn between two points on the surface of the particle. The source material 23 obtained as a result of the adhesion pretreatment step 22 may be in the form of a paste, ink, solution, dispersion or dry powder.
[0024]
If the starting material powder 20 or the particle size of such powder meets the size requirements, for example after sieving, a grinding process may not be required. For example, in some techniques such as spark erosion, fine powders containing Group IB-IIIA alloys may be produced in dielectric liquids such as water, or cryogenic alcohol or hydrocarbon liquids. . It is also possible to grind the various components of the starting material 20 separately and then mix the milled components to produce the starting material. For example, in the case of a starting material having only group IB-IIIA alloy-containing particles 31 and group VIA element particles 34, the powders of each of the two particle types may be separately prepared and ground. After the two powders are ground, the two powders may be mixed to produce the starting material.
[0025]
The source material 23 may further include an electrical dopant. These dopants may originate from the starting material, for example, may be present as one or more separate types of particle components in a mixture similar to the mixture of FIG. It may be included as a component of the alloy and mixed as another component of other particle components. Thus, of course, as one method, the dopant can be included in the form of an additional element powder or an additional powder containing a dopant compound, or even in a liquid. As shown in this example, such dopants can also be included in Group IB-IIIA-VIA compound films at other points in the process. Group IA and / or group VA elements can generally serve as such dopants.
[0026]
Referring to FIG. 2, a precursor film 25 is obtained by depositing a source material 23 on a substrate, which is in the form of a film by means of a film deposition process 24, and consists of two layers comprising sublayers and coating layers It may be a substrate. A variety of techniques can be used for the film deposition process 24. For the raw material 23 which is in the form of a paste, a screen printing technique can be used. If the source material 23 is in the form of an ink or paint, a number of wet deposition techniques known to those skilled in the art include spraying, painting with a brush, roller or pad, gravure printing, stamp printing, knife coating, cup coating and curtains. It can be used in the same way as a coating. If the source material 23 is in the form of a dry powder, it can be coated on the substrate using sprayed dry powder coating, including electrostatic spraying. In the case of an electroadhesive method, the dry powder particles may first have to be coated with a dielectric layer so that they can be electrically charged. The precursor film 25 should have a thickness greater than or equal to 0.5 μm and less than or equal to 20 μm, the preferred thickness range being greater than or equal to 1.0 μm, And less than or equal to 10 μm.
[0027]
As shown, assuming there are 32 separate Group IB particles and 33 Group IIIA particles, for example, at least 50 mole percent of the Group IB elements of the source material 23 and at least 50 moles of the Group IIIA elements. % Of one or more IB-IIIA alloys in small IB-IIIA alloy-containing particles distributed throughout source material 23 (eg, less than or equal to 2 μm) It is more preferable that it is contained in. This facilitates control and uniformity of the I / III ratio distribution of the final compound film 27 regardless of the uniformity of the substrate size or thickness of the precursor film 25 or compound film 27. Usually, higher mole percentages such as at least 60% in each case, at least 90% in each case, or 100% are advantageous from the standpoint of purely controlling this ratio and the uniformity of its distribution. Of course, this may include the complete absence of separate Group IB and Group IIIA particles.
[0028]
Still referring to FIG. 2, after its deposition, the precursor film 25 has undergone a post-deposition treatment step 26 to produce a compound film 27 of the IB-IIIA-VIA group. Post-deposition treatment step 26 includes a heat treatment that may be in the form of combustion furnace annealing at atmospheric pressure, vacuum annealing, rapid thermal annealing, or laser annealing. The atmosphere during the annealing process is vacuum, argon (Ar), helium (He) or nitrogen (N) (for example, N₂May be inert, such as hydrogen (H) (eg, H₂Or a VIA group element such as Se, S and Te. The exact characteristics of the annealing atmosphere in the post-deposition treatment step 26 depend on the characteristics of the source material 23. For example, if the source material 23 contains a suitable amount of a Group VIA element, the annealing atmosphere used may be inert or reduced. On the other hand, if the source material 23 does not contain any VIA group element or does not contain an appropriate amount, the annealing atmosphere is desired to produce a good quality IB-IIIA-VIA group compound film 27. Should contain elements of the VIA group.
In the case of selenide growth, the annealing atmosphere is H₂Se, (CH_Three)₂Se, (C₂H_Five)₂Se or Se vapor may also be included. H for sulfide growth₂S, CS₂Alternatively, S vapor may be used. In the case of a sulfide-selenide layer, a mixture of S and Se containing chemical species in an annealing atmosphere may be used, or one type of a Group VIA element such as Se may be included in the precursor film 25. Alternatively, the other type, such as S, may be supplied from the annealing atmosphere during processing step 26 after deposition. The annealing temperature may be in the range of 350 ° C to 700 ° C, with a range of 400 ° C to 600 ° C being generally preferred. The duration of the annealing depends on the temperature of the annealing, and this duration may vary from about 5 minutes to about 3 hours, and typically about 15 minutes to about 1 hour when combustion furnace annealing is used. Is preferred.
[0029]
In one embodiment of the present invention, the I / III molar ratio of source material 23 is greater than or equal to 0.80 and less than or equal to 1.0, and this ratio is determined in a substantially uniform manner. The material film 25 is transmitted. Referring to FIG. 2, in this case, the I / III molar ratio of the IB-IIIA-VIA group compound film 27 is very close to the I / III molar ratio of the source material 23. Alternatively, source material 23 having an I / III ratio higher than 1.0 and up to about 1.2 is, for example, Cu₁₁In₉Can be used to deposit a precursor film 25 having the same ratio. During the deposition process 26, additional Group IIIA materials can be added to the compound film 27, bringing its total I / III ratio to a desired range less than or equal to 1.0 (at the same time greater than 0.80). Large or equal to the desired range). If the layer of precursor film 25 contains at least about 80% Group IB elements and at least about 80% Group IIIA elements necessary to form IB-IIIA-VIA compound film 27, such a scheme Is practical. In particular, a very uniform delivery of additional group IIIA elements onto the precursor film 25 is required.
[0030]
【Example】
Example 1
The first example of the present invention used a Cu-In alloy starting material 20 powder obtained by melt atomization technique. Starting material 20 was obtained by mixing and melting 33.25 weight percent pure copper and 66.75 weight percent pure indium under a hydrogen curtain above 900 ° C. The Cu / In ratio of this melt corresponded to a molar ratio of 0.9. The molten alloy was converted to powder form in a gas atomizer using argon gas. The quenched powder was dropped into distilled water at the bottom of the reactor for further cooling. Powder starting material 20 was screened using a -625 mesh screen. Particle size analysis by conventional light scattering evaluation shows that after sieving, the powder consists of particles having a size ranging substantially from 1.3 μm to 20 μm, so that 20 μm or more is less than 0.3%. Indicated. X-ray diffraction analysis is based on Cu₂In, Cu₁₆In₉And possibly Cu₁₁In₉The presence of a Cu-In alloy phase such as In addition to the alloy phase, this starting material 20 had a separate phase. The starting material 20 of this example has no group IB element particles 32, no group IIIA element particles 33, and no group VIA element particles 34. The starting material 20 contained only IB-IIIA alloy-containing particles 31 containing a phase composed of the In element in addition to the IB-IIIA alloy. The selected Cu / In ratio was 0.9. In particular, it can be assumed that this molar ratio based on the initial weight percentage is usually achieved in the powder that is in the ink. Similar assumptions generally apply, for example, when this ratio is greater than about 0.8 and less than about 1.0, and is applied in these examples.
Source material 23 was made using the following adhesion pretreatment. The sifted 9.76 grams of powder was mixed with 22.62 grams of water. To the mixture was added 0.14 grams of wetting agent (W-22 manufactured by Daniel Products, NJ) and 0.39 grams of dispersant (D-3019 manufactured by Rohm & Hass, PA). The mixture was ground in a ball mill for 42 hours. The resulting raw material 23 was in the form of watery ink.
[0031]
For testing purposes, this ink precursor film (and thus no VIA present) is coated with a conventional piece of ready-made soda-lime glass cup coating technique. Such glasses typically contain about 15-17% sodium oxide (by weight). The cup used had an opening with a depth of 6 mils (150 μm) and the layer obtained after drying on a hot plate at 60 ° C. was about 20 μm thick. The X-ray diffraction analysis shown in FIG. 10 shows that CuIn marked with an asterisk₂Cu marked with phase and dot₁₁In₉X-ray diffraction spectrum showing the presence of. Particle size analysis by conventional optical scattering evaluation performed on the ink showed that the maximum particle size (maximum dimension at both ends) was about 2.0 μm and the average particle size was about 0.5 μm.
The above results demonstrated effective particle milling even in the presence of soft materials such as In. The described scheme as demonstrated in this example chemically bonds many of the Group IIIA elements (In) of the formulation to the Group IB elements (Cu) in the form of Cu-In alloys. Any extra In is finely dispersed throughout the small particles. Particles containing a Cu-In alloy phase and a finely distributed In phase can be efficiently ground as demonstrated in this example. This is probably due to the fact that Cu-In alloys are much more fragile than In. X-ray diffraction data shows that during the pulverization process, the finely distributed In further reacts with the Cu-In phase.₂It is shown that an alloy phase containing a lot of In determined to be is produced. Despite the fact that grinding was done in water, a clear amount of In₂O_ThreeWas not observed at all. This may be due to the fact that most of the In of the present invention is chemically bonded in the Cu-In alloy, and the oxidation of In in the alloy is as much as the oxidation of pure In elements. It is not preferable.
[0032]
Once the chemical species in the aforementioned precursor film are identified by the X-ray diffraction results of FIG. 10, the thinner film is used (as shown in 10 and 11 and in FIG. 3) using the same ink as described above. A) by a cup coating method on a two-layer substrate made of a glass substrate and a Mo coating layer. This method also uses one sheet of conventional ready-made soda-lime glass as a sublayer. As a result, the precursor film 25 is approximately 4 μm thick and is placed in a selenization reactor and 5% H₂Se and 95% N₂Annealed at about 450 ° C. for 15 minutes in the gas mixture. After cooling, the compound film obtained in this way was removed from the reactor and subjected to X-ray diffraction analysis. The obtained diffraction data is shown in FIG. All peaks in FIG. 11 show copper indium diselenide CuInSe, with the exception of two, which are related to the Mo coating of the substrate shown as Mo.₂Are related. This demonstrated the ability of the present invention to yield a group IB-IIIA-VIA compound. Furthermore, the substrate made of soda-lime glass with Na is CuInSe.₂Results in Na acting as a naturally-provided dopant, and as a result, no additional doping is required, even assuming that doping is desired. The concept of doping assumes that only a small percentage of the dopant is present in the doped material, but in general each added dopant has atoms replaced in the material or formulation. Less than about 1 mol% of atoms that can In fact, only a fractional portion of 1 mol% (typically less than about 1% of this 1%) is usually electronically active as a dopant for the material. Thus, for example, if a dopant is present in the starting material or source material as part of the IB / IIIA alloy phase, this phase may be combined with a doped IB-IIIA alloy phase having the dopant in a small percentage composition. It is regarded.
[0033]
Example 2
In another example, the first example starting material 20 powder comprises 9.78 grams of screened powder, 22.4 grams of water, 0.14 grams of W-22, 0.39 grams of D-3019 and 0.1 grams of Used in a mixture with Se powder. The mixture was ground in a ball mill for 42 hours. The resulting raw material 23 was in the form of water-filled ink. The precursor film 25 obtained by this method was deposited by the same cup coating technique using the ink source material 23 as in the first example of the same shape as the double layer glass / Mo substrate. The resulting precursor film 25 was about 4 μm thick. The resulting precursor film 25 is placed in a selenization reactor and treated with 5% H for 15 minutes.₂Se and 95% N₂Annealed to about 450 ° C. in a gas mixture. According to the X-ray diffraction data of the resulting layer, the compound film 27 is converted into CuInSe.₂Identified. This example was repeated by increasing the Se amount to 3.04 grams, reducing the water to 22 grams and reducing the starting material powder to 6.61 grams. CuInSe₂Production was confirmed by X-ray diffraction data. However, this film was more porous when compared to a film prepared with only 0.1 grams of Se.
[0034]
Example 3
In the third example, the melt atomization technique of the first example (followed by a sieving step) is used for other starting materials having different compositions of 50.78 weight percent In, 36 weight percent Cu, and 13.22 weight percent Ga. Used to obtain substance 20 powder. This composition corresponds to the molar ratio of Cu / (In + Ga) = 0.9 and Ga / (Ga + In) = 0.3. Here, the element of group IB is Cu, and the group IIIA has the chemical formula In when 0 <x <1_xGa_(1-X)It was an alloy or mixture of In and Ga that can be represented by In this example, 11.03 grams of the resulting starting material 20 powder was ball milled for 42 hours in a mixture of 25.03 grams of water with 0.16 grams of W-22, 0.44 grams of D-3019 and 0.11 grams of Se powder. Crushed. Ink raw material 23 obtained as a result of the grinding process had agglomerated particles, which were crushed by a mortar and pestle. This ink was applied with a brush on soda lime glass (using the same ready-made soda lime glass material containing Na as in the first example). The selenization process of Example 1 was performed on the resulting layer. X-ray diffraction data is CuInSe₂Phase and CuIn_0.7Ga_0.3Se₂A peak related to the phase was shown.
[0035]
Example 4
In yet another example, a single CuInSe formed on a glass / Mo substrate according to the first example.₂The film is prepared using CuInSe using standard procedures known in the art.₂Used for the production of / CdZnS solar cell devices. A thin layer of CdZnS is formed by CuInSe by commonly used chemical bath deposition techniques.₂Attached on top. The deposition bath consists of 5 ml 0.5 mol zinc acetate, 10 ml 1.0 mol cadmium acetate, 7 ml triethanolamine, 4.5 ml ammonium hydroxide and 55 ml distilled water. The solution was heated to 55 ° C. and the sample was placed in a beaker containing the solution. 12 ml of 1.0 molar thiourea was added into the beaker to initiate CdZnS deposition that lasted 10 minutes. CuInSe₂As the film is immersed in the bath, this adhesion causes CuInSe₂An extra layer of CdZnS was deposited on the back of the film, which was removed using a cotton swab soaked in HCl. CdZnS deposition is followed by deposition of a transparent ZnO layer by commonly used metal organic chemical vapor deposition (MOCVD) techniques using diethyl zinc as the zinc source and water vapor as the oxygen source. The sheet resistance of the ZnO layer was about 10 ohms per square. 0.09cm²The solar cells were separated and characterized. FIG. 12 shows the current versus potential (IV) characteristics of a typical device made by this method and has a conversion efficiency of about 7%. This result demonstrates that this method has the ability to produce materials with electronic properties suitable for the production of active electronic devices.
[0036]
Example 5
In yet another example, the melt atomization technique was used to obtain a powder of other starting material 20 having a Cu / In molar ratio of 0.87, which was screened as in Example 1. Ink raw material 23 having the same Cu / In ratio was obtained after grinding using this sieved powder, as shown in the first example. This source material 23 was coated onto a Mo-coated glass substrate (using the same ready-made soda-lime glass material containing Na as in the first example) using the same cup coating technique. As shown in Example 1, a selenization process was performed and the solar device was manufactured as described above in Example 4. FIG. 13 shows the IV characteristics of a typical solar cell obtained, with a conversion efficiency of 9.42%.
[0037]
Example 6
In order to demonstrate doping of the compound film externally rather than by diffusion from Na-containing glass, the following experiment was conducted.
The ink of Example 5 was coated on a glass / Mo substrate. The glass selected this time was Corning 7059 glass which contained no Na. By choosing a glass substrate that does not contain Na, it was ensured that any doping effect that could be observed would not diffuse Na from the glass through the Mo contact layer into the compound layer.
In addition, a 6 ml portion of Example 5 ink was placed in a small tube and 42 mg of sodium acetate was dissolved in this ink. The doped ink was then coated onto a glass / Mo substrate using Corning 7059 glass.
The precursor layer with added impurities and the precursor layer without added impurities were selenized as in Example 1. The device was fabricated on both films as in Example 4. This result is shown in the two IV curves shown in FIG. Curve “A” equipment made with compound films without added impurities does not perform very well with conversion efficiencies less than 0.5%. This is CuInSe₂This is due to the very high resistivity of the layer. The curve “B” device made with the compound film doped with impurities has a significantly improved efficiency of 4.5%, demonstrating the efficiency of exogenous Na doping. Similar practical results are utilized using other Na dopant sources such as sodium sulfate and sodium sulfide.
[0038]
The basic method described is expected to be practical, with the group IB element versus the group IIIB element in a compound film greater than or equal to 0.5 and less than or equal to 1.0. Produces remarkably practical results having a mole percent ratio. As this ratio increases, this result should improve accordingly, and it is generally more desirable to be greater than or equal to 0.80 and less than or equal to 1.0. The use of doping to some extent can compensate for the lower end ratio. Thus, an I / III ratio of, for example, 0.6 with doping is expected to give results comparable to a significantly higher ratio without doping. Furthermore, as already indicated, an onset or intermediate ratio greater than 1.0 but reduced to less than 1.0, for example, until the end of the annealing process can be achieved, so that an onset ratio of up to 1.2 is practical. Expected to have remarkably practical results.
The described method has a range of applications, for example from large scale solar cells for power generation to small device components such as medical sensors. Manufacturing large devices of at least 1 square foot and preferably 4-8 square feet is based on high yield efficiency results such as about 10% and at least 7%. After all, the 15% efficiency of large modules is not surprising.
[0040]
Of course, numerous changes and modifications may be made in the method and apparatus depending on the particular situation and application without departing from the spirit or scope of the invention as defined by the following claims and their equivalents. It is readily apparent that
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a solar cell made according to the present invention.
FIG. 2 is a flow chart illustrating the steps of the method used to grow a IB-IIIA-VIA group compound thin film according to the present invention.
FIG. 3 is a schematic diagram showing the composition of the starting material according to the present invention.
FIG. 4 diagrammatically shows Group VIA particles in powder form mixed with powder containing Group IB-IIIA alloy-containing particles.
FIG. 5 schematically illustrates the removal of particles larger than a predetermined size from the mixed powder of FIG.
FIG. 6 schematically illustrates a powder having only smaller particles mixed in a liquid as a process of forming ink.
FIG. 7 schematically illustrates a liquid-containing powder that undergoes grinding to form an ink.
FIG. 8 schematically illustrates crushed ink deposited on a large area substrate.
FIG. 9 schematically illustrates a substrate having deposited ink that is exposed to an atmosphere containing a Group VIA element and heated to form a Group IB-IIIA-VIA compound film on the substrate.
FIG. 10 shows X-ray diffraction data obtained from a precursor film made in accordance with the present invention.
FIG. 11: CuInSe made according to the present invention₂2 shows X-ray diffraction data obtained from a film.
FIG. 12 shows CuInSe grown according to the present invention.₂Fig. 5 shows the illuminated IV characteristics of the solar cell produced above.
FIG. 13 shows IV characteristics of a solar cell manufactured according to another embodiment of the present invention.
FIG. 14 shows IV characteristics of a solar cell manufactured according to still another embodiment of the present invention.

Claims (28)

In a method of producing a compound film,
(A) supplying a starting material comprising a powdery substance having a group IB element and a group IIIA element;
(B) a raw material comprising IB-IIIA group alloy-containing particles having at least one IB-IIIA group alloy phase from the starting material, wherein the IB-IIIA group comprises an IB group element in the raw material and Preparing more than 50 mol% of each of the group IIIA elements;
(C) depositing said source material on a base in the form of a precursor film;
(D) The precursor film is heated in a heat treatment atmosphere corresponding to the composition of the constituent material to produce a film containing a IB-IIIA-VIA group compound, thereby producing a compound film. Method.   The method for producing a compound film according to claim 1, wherein the ratio of moles of group IB elements / group IIIA elements in the raw material is larger than 0.80 and smaller than 1.0.   The method for producing a compound film according to claim 1, wherein a ratio of moles of group IB elements / groups of group IIIA elements in the raw material is greater than 1.   The method for producing a compound film according to claim 3, wherein the ratio of the number of moles of group IB elements / number of moles of group IIIA elements in the compound film is larger than 0.80 and smaller than 1.0.   The compound film according to claim 1, wherein the IB-IIIA group alloy is more than 60 mol% of the IB group element of the raw material and more than 60 mol% of the IIIA group element. how to.   The compound film according to claim 1, wherein the IB-IIIA group alloy is more than 90 mol% of the IB group element of the raw material and more than 90 mol% of the IIIA group element. how to.   The method for producing a compound film according to claim 1, wherein the IB-IIIA alloy-containing particles contain at least one group IB or IIIA element phase.   The method for producing a compound film according to claim 1, wherein the raw material further includes particles having a group IB element phase.   2. The method for producing a compound film according to claim 1, wherein the raw material further includes particles having a group IIIA element phase.   The method for producing a compound film according to claim 1, wherein the raw material further contains group VIA-containing particles.   The method for producing a compound film according to claim 1, wherein the step of supplying the starting material includes producing a powder composed of the IB-IIIA alloy-containing particles.   2. The method of producing a compound film according to claim 1, wherein the powder aggregate of the raw material in the preparation step following the supplying step is substantially composed of particles having a particle size of less than 20 microns.   2. The method for producing a compound film according to claim 1, wherein the powder aggregate of the raw material in the preparation step is substantially composed of particles having a particle size of less than 2 microns.   The method of producing a compound film according to claim 1, wherein the precursor film is a single layer.   The method of producing a compound film of claim 1, wherein the compound film is thicker than 0.5 microns and thinner than 20 microns.   The method of producing a compound film according to claim 15, wherein the compound film is thicker than 1 micron and thinner than 10 microns. The step of supplying the starting material comprises the step of supplying a powder of the IB-IIIA group alloy-containing particles, and the preparation step includes the step of generating an ink containing the group IB-IIIA alloy-containing particles from the starting material. A method for producing a compound film according to claim 1.   2. The method for producing a compound film according to claim 1, wherein the IB-IIIA alloy-containing particles contain a Group IIIA material selected from Group IB Cu and In or Ga.   The IB-IIIA alloy-containing particles include a Group IIIA material made of an alloy of In and Ga represented by the chemical formula InxGa (1-X) (where X is greater than 0 and less than 1). The method for producing a compound film according to claim 18.   The method for producing a compound film according to claim 1, wherein the IB-IIIA alloy-containing particles are dispersed throughout the raw material.   The method of producing a compound film according to claim 1, wherein the alloy phase includes a dopant.   The method for producing a compound film according to claim 21, wherein the dopant is an element selected from Na, K and Li.   The method for producing a compound film according to claim 1, wherein the raw material contains a dopant.   The method of producing a compound film according to claim 1, wherein the compound film comprises a dopant. A method of manufacturing an electronic device comprising:
(A) supplying a starting material comprising a powdery substance having a group IB element and a group IIIA element;
(B) a raw material comprising IB-IIIA group alloy-containing particles having at least one IB-IIIA group alloy phase from the starting material, wherein the IB-IIIA group comprises an IB group element in the raw material and Preparing more than 50 mol% of each of the group IIIA elements;
(C) depositing said source material on a base in the form of a precursor film;
(D) An electronic device comprising the step of heating the precursor film in a heat treatment atmosphere corresponding to the constituent material composition to produce a film containing a compound of the IB-IIIA-VIA group is manufactured. Method.   The step of supplying the starting material comprises the step of supplying a powder of the IB-IIIA group alloy-containing particles, and the step of preparing generates an ink containing IB-IIIA group-containing particles from the starting material. 26. A method of manufacturing an electronic device as claimed in claim 25.   27. The method of manufacturing an electronic device according to claim 26, wherein the powder aggregate of the raw material in the preparation step following the supply step is substantially composed of particles having a particle size of less than 20 microns.   27. The method of manufacturing an electronic device according to claim 26, wherein the powder aggregate of the raw material in the preparation step is substantially composed of particles smaller than 2 microns in particle size.

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