TW201109458A - Sintered cu-ga alloy sputtering target, method for producing the target, light-absorbing layer formed from sintered cu-ga alloy sputtering target, and cigs solar cell using the light-absorbing layer - Google Patents

Abstract

Disclosed is a sintered Cu-Ga alloy sputtering target which is characterized by being composed of a sintered body of a Cu-Ga alloy powder that has a Ga concentration of 20-60 at% with the balance made up of Cu and unavoidable impurities. The sintered Cu-Ga alloy sputtering target is also characterized in that the sintered body has a relative density of not less than 97%, an average crystal grain size of 5-30 μ m and an oxygen content of not more than 400 ppm. It is also effective for the sintered Cu-Ga alloy sputtering target to have an oxygen concentration of not more than 400 ppm and a uniform composition. The target may be produced by a powder production method and hot pressing method of a starting material powder. The Cu-Ga target is free from compositional segregation and no particle adheres to a film that is obtained by sputtering after long-time sputtering. Also disclosed is a method for producing the sintered Cu-Ga alloy sputtering target.

Description

201109458 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method of forming a Cu-In-Ga-Se (hereinafter referred to as CIGS) quaternary alloy thin film (i.e., a light absorbing layer of a thin tantalum solar cell layer). Cu-Ga alloy sintered body sputtering target used, a method for producing the same, and Cu-Ga

A light absorbing layer made of an alloy sintered body and a CIGS 糸 battery using the light absorbing layer. [Prior Art] In recent years, mass production of CIGS-based solar cells having high efficiency as thin-film solar cells is progressing, and a method of producing a light-absorbing layer is known as a method of selenium plating and selenization. Although the solar cell manufactured by the vapor deposition method has the advantages of high conversion efficiency, it has the disadvantages of low film formation speed, high cost, and low productivity, and the selenization method is more suitable for mass production in the industry. The general procedure of the deuteration method is as follows. First, a molybdenum electrode layer is formed on a soda lime glass substrate, and a Cu-Ga layer and an iι layer are formed by sputtering thereon, and then a CIGS layer is formed by high temperature treatment in a hydrogenated selenium gas. Cu-Ga dry is used in the sputtering film formation of the Cu_Ga layer in the CIGS layer forming process by this selenization method.

The manufacturing method of the Cu-Ga target includes a melting method and a powder method. In general, the Cu-Ga target produced by the melting method has less impurity contamination, but has problems such as large composition segregation and a decrease in yield due to a shrinkage cavity. The target produced by the powder method has a sintered density. Low, high oxygen concentration and other issues. Various factors will affect the conversion efficiency of CIGS solar cells, and the characteristics of cms film will also have a great impact, forming the characteristics of the cigs "Cu-Ga film in the pre-201109458 phase will also affect the conversion efficiency of solar cells. The target obtained by sintering the powder has less component segregation than the melted product, and is easy to manufacture, and A is easy to adjust the composition as needed. The feature 'has a greater advantage than the refined product. "However, the dryness obtained by sintering has problems in that particles are easily generated. In particular, if there is foreign matter such as particles on the surface of the film, the subsequent (10) film characteristic band = adverse effect will eventually lead to a significant decrease in the conversion efficiency of the CIGS solar cell. The cause of the particles is abnormal discharge during sputtering, which is related to the density of the target. Further, since the powder is used, there is a tendency that oxygen or oxygen is mixed into the powder to form a high oxygen concentration. k 王 a 马 记载 记载 记载 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰 艰The reason for this is as follows. In this document, the Cu-Ga target system is produced by a melting method. However, the density is high, and the passage of the passage [0010J ' does have such a body. The melted product is compared with the sintered product. The density is often less than 100%. However, the patent document describes the density of the "high density of 95% or more relative density". However, 'relatively dense' is about 95% and cannot be called high density. In fact, in our patent document, in the patent document, pores and poor pores (voids) which reduce the density are generated in the mouth. However, it has not been disclosed at all. Only the description has been made. Although the description of the composition segregation has not been observed, the analysis results and the like are shown. From the above-mentioned degree of relative density, the increase in seizure of the level of cognition is described. 201109458, and the ° melting method usually constitutes a large segregation, because it has not undergone a special step to eliminate segregation, and the township will have a general degree of segregation. This kind of dazzling product special right eve # >, there is a segregation of the film composition changes in the sputtering process. The conditions of enamel plating are also unknown. _In the beginning of enamel plating, even if there is no abnormal discharge, etc., it may cause abnormal discharge due to the occurrence of sputtered surface roughness, etc. 'This is a well-known fact that is about the long-term sputtering. There is no record of whether there is no different suspension discharge or particle spawning. Further, in the case of #AU-V ^1 / ^ in Cu-Ga dry, and in his literature (Patent Document 2), it is described that the body is burnt, and when it is a cutting target, it is easy to be broken and the brittleness of the defect. In order to solve this problem, two types of powders were produced and mixed for sintering. One of the powders is a powder of γ r 人 日 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 Coexisting organization: This step is because the manufacturing process is two-injection of φ powders, so the steps are complicated, and the hardness and other physical properties of the powders are different, and the microstructure is different, _., ^3, so only the sintered body is difficult to form a sintered body. 'Can't expect an increase in relative density. The target with a lower density will of course have a discharge to the μ s$ and a particle, and if there is a foreign matter such as particles on the surface of the film, the film properties will also be affected by the subsequent (10) film characteristics. The conversion efficiency is large. In Patent Document 2, although the bran is not used, the Wojin is coated with a target, and the abnormal discharge and the particles are not contained, but it can be said that 1 201109458 is implied. problem. In Patent Document 3, 'the material of the recording layer of c is exemplified, and the ice is used as the recording medium of the prior art. However, it is also inorganic...7 = the layered Auzn recording layer is sputtered. '..., but it implies that in the patent document 4 of the CuGa2 patent, there is no CUGa2 as the material of the δ recording layer of the optical recording medium. 5 layers of the AuSn recording layer were deposited by sputtering. There is no splash of CuGn ·> Seven along the Yankuang Mine. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The homogenous property has a standard deviation of less than 15%. The purpose is to make the Ga concentration low and to make a specific texture by forging and calendering. Patent Document 6 proposes a copper alloy in which 3 Ga of added halogen is added to the solid solution limit of Q1 to (4) (4). However, the examples shown in the examples are only Cu_Mn alloys, and the method for the production of the crucible is not specifically described, and it is considered that the crucible is obtained by the melting method. The purpose is for display devices. Patent Document 7 describes a method for producing a target using a mixture of indium powder and Cu-Ga alloy powder as a raw material for a copper alloy target obtained by subjecting a raw material component of a powder to a water pressure compression. . Compared with the present invention, sintering is not performed, and the composition is different, and there is no relevant element. Patent Document 8 describes a sputtering sputter containing a 1 to 2 〇 at% Gai Cu alloy recording layer. However, in the examples, an arc dissolving furnace melting 6 201109458 is used to prepare a material in which Cu is added with Mn or Mn. It can be used as an ingot for any specific description of the dry copper alloy to which Ga is added. In the patent document 9, the use of CuGa for the use of Ga, which is used for the production of CIGS-type thin film solar cells, 10, 2, 3, 3, and 3, and 30% by weight of Ga is described. For example, there is no record of the method of making the CuGa Hejinshi & Gold target itself. Further, the characteristics of the target are also not described in the same manner. Patent Document 1G towel describes a method of producing a CUGa alloy containing 25 Å by a forging quenching method. Although it is invented in the present invention, it is a thin-film solar cell application, but it is a problem that is unique to forging, and the problem solved by the invention of the present application still exists. Patent Document 11 defines a c-alloy target of 2G to 96% by weight of 11 and it is described that Ga25 wt% and Cu75 wt% are particularly effective in the examples. However, there is no record in the production method of the "9cu_Ga" book itself. The characteristics of the book are also not recorded. The above-mentioned patent

The disclosure of the subject matter of the present invention and its solutions can be found in the literature. X Patent Document 1 Patent Document 2 Patent Document 3 Patent Document 4 Patent Document 5 Patent Document 6 Patent Document 7 Patent Document 8 曰本特开 2000-73 No. 163 曰本特开 2008-138232号曰本特开昭63 Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Among the Cu_Ga sintered body, the density is high, and there is almost no abnormal discharge at the time of quenching after a long period of time, the Cu_Ga alloy sintered body in which the particles are generated from the film, the manufacturing method thereof, and the sintering by the Cu-Ga alloy. The light absorbing layer produced by the body cavity and the CIGS solar cell using the light absorbing layer. In order to solve the above problem, the inventors of the present invention have worked hard to find out that abnormal discharge, particle generation, and density are closely related, and that the problem of low density and abnormal discharge and particle increase occurs, and the problem is obtained. Improve the average particle size of the dry, oxygen concentration, composition of the sentence, etc., and further increase the CIGS layer formation process library 夕 p p in the sister (1) layer of the sputtering film formation characteristics, help the solar cell The present invention has been completed by the insight of the conversion efficiency. That is, the present invention is composed of a sintered body in which 1 is 20 to 60 at%, the remainder is - and an unavoidable impurity is obtained, and the relative density of the sintered body is 97 /. The above, the average crystal grain size is 400 Ppm or less; 3〇Am, and the oxygen content is 2), such as 4 υ of the Cu-仏 alloy sintered body (10), which is such that the c sheet metal is composed of a single composition; a 3) Cu~2) The Cu_Ga alloy sintered body of any one of the υ~2) 201109458 2222 & alloy X-ray diffraction of the external peak intensity relative to the main peak intensity of 5% or less; as above 4 丨) ~ 3) In the CU'Ga bismuth sintered body of any of the items, the composition of the Cu-Ga alloy is substantially 7 phases or the main phase is the r phase. Further, the present invention provides a method for producing a Cu_Ga alloy sintered body sputtering target, which is obtained by melting and cooling a raw material of Ga and Ga, and then grinding the σ raw material powder into a Cu_Ga alloy by hot pressing. A method of plating a target, which is characterized by: The holding temperature during hot pressing is set to be lower than the melting point of the mixed raw material powder by 5 〇 2 2 ° C, and the holding time is set to be 3 hours, and the cooling rate is set as the generation/thesis = the upper part is pressed against the mixed raw material powder. The pressure is set to 30 to 40 MPa to carry out heat 6) a method for producing a Cu-Ga alloy sintered body sputtering target, which is to smash and cool the Cu and Ga raw materials, and then pulverize the kiln by hot pressing A method for producing a Cu_Ga alloy sintered body sputtering target according to any one of the above-mentioned 丨) to 4), which is characterized in that: 疋... The holding temperature during hot pressing is set to be lower than the melting point of the mixed raw material powder by ~2 〇〇 ° C, and the holding time is set to be 3 hours, and the cooling rate is set as "above, the pressing pressure of the mixed raw material powder is set to 3" 〇〜4〇Μρ& to perform hot pressing; ,, ', 7) The method for producing a Cu_Ga alloy sintered body sputtering target according to the above 5) or 6) is carried out by gas atomization or water atomization Cu and ~ are pulverized after melting and cooling. Further, the present invention provides 201109458 8) a light absorbing layer which is produced by the Cu_Ga alloy sintered body sputtering target of any of the above 1) to 4) A Cu-Ga-based alloy film is formed; 9) A CIGS-based solar cell using the light-absorbing layer of the above 8). According to the present invention, a Cu-Ga sintered body can be provided in the ore-reducing dry, without composition Segregation, and no abnormal discharge after long-time sputtering, Cu_Ga alloy sintered body target which produces almost no particles on the film obtained by splashing, and a manufacturing method thereof, thereby improving the manufacturing yield of the Cii-Ga film while suppressing The conversion efficiency of the cms solar cell made of the Cu-Ga film is excellent. EMBODIMENT Next, the reason for the definition and scope of the constituent elements of the present invention, the meaning, the adjustment method, and the measurement method for describing the form of the invention are described. The remaining part of the invention is Cu and an unavoidable impurity. The thought itself can also be applied to the group of relatively dense Helmets and lionesses outside the range, which will be burned to more than 4. The relative density is the target of the sintered body.

Hu's theoretical density obtained by #: the low density of the phase field means that there are a large number of internal voids in the dryness, so when the inner Zoukong hole appears in the town, "it is easy to produce a hole around the hole: 10 201109458 aircraft, abnormal discharge. The occurrence of particles in the film is increased, and the surface roughness is prematurely caused by surface protrusions (n〇 (juie) as a starting point', lifting discharge, etc. This is a reduction in conversion efficiency of CIGS solar cells. One of the reasons. Therefore, the relative density of the sintered body target must be at least 97%, preferably 98% or more, more preferably 99% or more. Furthermore, the Cu_Ga alloy sintered body sputtering target of the present invention will have an average crystal grain. The diameter is set to 5 to 3 〇//m. The average particle size can be slightly etched as needed to make the sunday boundary clear and then determined by the planimetric method. If the average particle size of the sintered body target is small, it has Further, if the average particle size is large, the crystal grains of the shell and the bismuth will be randomly aligned, and therefore the sputtering speed will be different depending on the orientation of the crystal plane, so that it is easy to generate large irregularities on the surface, and it is easy to increase This is the starting point Therefore, by making the average particle diameter smaller, the density of the target can be increased, and the number of particles generated can be further reduced. From the above mechanism, the average crystal grain size of the target is as small as 5 to 3 〇 The m or so will have a large advantage. However, if the average particle diameter is less than 5 claws, it is disadvantageous to be practical because the steps must be further increased in manufacturing. Therefore, the lower limit of the average crystal grain size is set to 5 m. Moreover, if the average particle size exceeds 30 A m, the effect of density increase is reduced, and the number of particles is increased, so it is preferable to set it to 3 〇# m or less. The average particle diameter can be adjusted according to the temperature at which the heat is maintained. The higher the temperature, the larger the particle size. Although X' can be further 353-, or even larger than 50, it is not good because of the density reduction. 201109458 The amount of oxygen is 4~ As a condition for the sintered body to be dry, if the oxygen concentration is high, the metal components are combined to form an oxide. Moreover, the metal is higher than the single-component resistance. There is a difference in resistance in the gold, which is easy to occur. High resistance:: is: and dry: Causes of abnormal particles on the surface of the surface due to different discharge and reduction. Gu Yi becomes abnormal discharge, and the environment: the mechanical concentration will increase the oxygen concentration. When pouring: ..., it is necessary to reduce the pulverized powder to the opposite side. If it is made in an *oxygenated environmental towel, the atomization method and the gas atomization method can reduce the oxygen concentration. Treatment....The body atomization method is better. It is better to extract the Cu-Ga alloy sintered body as the best condition for the ore-reducing dry--, == one gold...the composition of the alloy is burnt.

In the present invention, the term "composition" is composed of "only a component such as A segment which cannot detect the presence of other components: use is used. Also, microscopically, even if a trace is contained, it is considered to be oxygenated. The thorns *々/, he, and the same or not - s have a bad effect on various characteristics of a single township and the same effect. The permeation will still show the best conditions for the sputtering of the Cu-Ga alloy sintered body (4), ', Cu'Ga alloy sintered body sputtering target, the Cu-Ga alloy χ 12 201109458 ray diffraction The peak intensity other than the main peak is 5% or less with respect to the main peak intensity. The basis of the singularity can be defined by the X-ray peak intensity ratio. Compared with the main and the peaks, the intensity of the peaks of other components can be substantially the same as the single composition. The composition of the mixed raw material powder produced by the gas atomization or water atomization method is substantially uniform. The (four) composition obtained by hot pressing the raw material for the occupation may also be close to the uniform sentence. Further, if the cooling rate in the cooling of the hot house is small, a hetero phase may be precipitated during cooling. If the amount of such out-of-phase is large, it can be detected by the ray diffraction peak. The cu-Ga alloy has a Gamma (1) phase when its composition is about 3 〇 to gamma. This phase is brittle and has the characteristics of being easily broken. CIGS is used in solar cells. It is especially suitable for this Ga concentration. It is particularly effective to avoid the enthalpy of this Cu-Ga alloy. The method of manufacturing the target of 'Nei Nai' describes the reasons and tolerances of the scope, the effects on the characteristics of the stem. After weighing the original steel crucible with a predetermined composition ratio, it is placed in a heating furnace of carbon 坩 45 () to about Ο · 5 ^ atmospheric pressure to refine the mixed raw materials. Keep about = the minutes to mix the molten raw materials', and fill the primary synthetic raw materials. After the τ was heated, after cooling, the synthetic raw material was taken and pulverized to obtain a micro (four) material. The pulverizing side has mechanical pulverization, gas atomization method, and water atomization method. However, any method can be used, which is comparable to the cost and can be handled by a large amount of water atomization method. In the case of water atomization, the method is dazzled in the crucible: ^ The crucible-grade synthetic raw material is re-dissolved, so that it becomes a liquid-like raw material droplet, and the dropping liquid

13 & 201109458 Spray about 1 mppa of the same ancient pressure to the same pressure water to obtain fine powder. The obtained fine powder is used as a raw material of the micropowder after being subjected to pressure rolling, drying, etc., and θ. The mixed fine powder material is passed through a sieve of a specific opening, and the particle size distribution is adjusted, followed by hot pressing. The hot pressing conditions vary depending on the Ga concentration, for example, when

When the Ga concentration is 30 at%, the temperature is _~ bribe, and the pressure is about 3 〇 to 40 MPa. That is to say, in terms of the preferable conditions of the hot pressing, the effective ones are as follows: the holding temperature of the crucible (4) is lower than the melting point of the mixed raw material powder, and the cooling rate is set to 51/min or more when the holding time is 3丨. ' The pressure of the mixed raw material powder is set to 3G to side Pa. When this money condition is properly selected, the density of the Cu-Ga alloy can be increased. In terms of the relationship between the temperature rise rate and the holding time, such as the temperature profile and the pressure application profile, (4) after the temperature is set to the highest temperature and then the pressure is applied, the pressure is applied first. Before the knot, the raw material powder will be finer and finer, so it is effective for increasing the sintered density. If the cold rolling speed of hot pressing is slow, there will be a heterogeneous phase between them, so the cooling rate is more than 5 t/mln. Fast temperatures are effective. The density of the cu_Ga sintered body produced by the above method can be determined by the Archimedes method, the average particle diameter can be obtained by surface etching, the plane method, the oxygen concentration can be ICP scooping, and the composition can be obtained by X-ray diffraction. The Cu-Ga sintered body can be processed into, for example, a diameter of 6 吋 and a thickness of 6 mm, and then indium is attached to a backing plate as a brazing filler metal as a sputtering target, and then a film is formed. Investigate the state of particle generation, ball formation, and abnormal discharge of film 201109458. EXAMPLES Next, examples and comparative examples of the present invention will be given. Further, since the following examples are not representative of the examples, the present invention is not necessarily limited to the embodiment of the invention, which should be explained in the scope of the technical idea described in the specification. (Example 1) A scale of $Cu raw material and Ga raw material so that the composition has a Ga concentration of 3 〇 at%, placed in a carbon steel pile, dissolved in c in a heating furnace to which 5 Mpa of nitrogen is applied, and then cooled. Quickly smash 5~1 (after rc/min cooling, take out the synthetic raw material. Then, put the synthetic raw material in the carbon crucible of the water atomizing device, melt it at °c, drop the molten solution and spray 1〇Mpa for the dripping liquid. The high-pressure water is obtained, and the Cu-Ga mixed fine powder is obtained. The mixed fine powder is subjected to pressure filtration and dried at 12 ° C. The mixed fine powder raw material is obtained, and the mixed fine powder is heated from room temperature to 65 at a heating rate of 5 C /min. After 〇 ° C, a pressure of 35 MPa was applied while maintaining at 650 ° C for 2 hours. Thereafter, after cooling at a cooling rate of 5 C /min, the burned scorpion was taken out. The relative density of the obtained Cu-Ga sintered body was 99. 9%, the average particle size is 5 V m, the oxygen content is 350 ppm, and the intensity ratio of the main phase and the heterogeneous X-ray diffraction peak is 0.2%. The sintered body is processed into a disk shape of 6 n in diameter and 6 mm in thickness. Sputtering target is used for sputtering. The sputtering power is DC (1000), and the ambient gas is argon. Amount 50 sccm, a pressure 〇.5Pa when using sputtering, the substrate having a diameter of 4 inches and a thickness of the square Corning 1737 glass substrate of 7mm.

B 201109458 After the sputtering time of 20 hours, the total sputtering amount was 20 kWhr, and the number of particles generated at a thickness of 0.2/m or more of the film when the Cu-Ga film thickness was formed by a microscope for 30 minutes was counted by a microscope. Further, no abnormal discharge was observed at the time of film formation. The above results are shown in Table 1. Table 1 Example Ga concentration (at%) Relative density (%) Average particle diameter (rotation) Oxygen content (ppm) X-ray intensity ratio (%) Number of particles (number) Abnormal discharge Example 1 30.0 99.9 5 350 0.2 0 None Example 2 30.0 99.8 12 360 0.3 0 No Example 3 35.0 98.8 19 390 0.5 2 No Example 4 35.0 98.6 20 390 0.8 1 No Example 5 42.6 97.8 25 400 1.0 5 No Example 6 42.6 97.5 26 400 1.2 8 None Comparative Example 1 30.0 97.2 24 420 0.9 11 Less Comparative Example 2 30.0 97.0 25 420 1.0 12 Less Comparative Example 3 30.0 98.0 20 450 0.8 13 Less Comparative Example 4 30.0 98.6 15 450 0.4 16 Comparative Example 5 30.0 97.5 25 450 1.0 17 Comparative Example 6 30.0 97.8 24 470 0.9 18 Comparative Example 7 30.0 98.5 18 470 0.5 17 Comparative Example 8 30.0 98.1 14 480 0.4 19 Multi-Car Example 9 30.0 97.8 25 600 1.0 20 Comparative Example 10 30.0 97.6 28 1300 1.5 25 Comparative Example 11 30.0 98.6 50 350 4.6 15 Less Comparative Example 12 30.0 98.6 28 350 7.0 19 Less Comparative Example 13 30.0 98.2 97 350 11.0 21 Multiple Comparative Example 14 30.0 99.9 1100 40 18.8 28 Multiple Comparative Example 15 35.0 98.0 960 50 17.5 24 more comparative examples 16 42.6 95.8 830 50 15.0 22 Comparative Example 17 30.0 95.0 13 360 0.2 22 Comparative Example 18 30.0 90.0 15 360 0.2 50 (Example 2 to Example 6) In the same manner as in Example 1, the composition of Ga was separately prepared. The results of the sputtering evaluations of the targets which were changed with the average particle diameter are shown in Table 1.

16 201109458 As shown in Table 1, the range of 42 at% in Example 2 and the average particle diameter were in the range of 400 ppm. The Ga concentration in Example 6 was 3 〇 12 to 26 / z m, and the oxygen content was 36 Å. Further, the average crystal grain size was adjusted by adjusting the sintering temperature, pressure, and cooling rate. Further, the oxygen content can be controlled by the adjustment of the melting environment of the raw material. When the crystal grain size of the sintered body is fine, the density tends to be high. In Tables 1 to 2, the relative densities of Examples 2 to 6 are in the range of 99 8 97 5 , the X-ray intensity ratio is in the range of 0.3 to 1.2%, and the number of particles is in the range of 0 to 8 without abnormal discharge. table! In the case of the case where the Iri is often discharged, it is described as "None", and the case of the case of the first time is described as "Less: If the number is more than 10 times, it is described as "More than this Table 1 is clear". The diameter is dry within a certain range, and no abnormal discharge occurs, and there is almost no generation of particles on the film, which is a good result. Although the main reason for this is that the oxygen concentration is large in the middle field, it is also double to the sintered body. The influence of the average crystal grain size and density. This tendency is clear from the comparison with the comparative examples shown below. (Comparative Example 1 to Comparative Example 2) "Established under the same conditions as the actual column {A1" & However, changing the melting atmosphere of the raw material to oxygen is more than the conditions of the examples. Therefore, the oxygen s of the sintered body is more than the conditions of the present invention. Further, the density was slightly lower than that of the example by making the temperature at the time of hot pressing lower than the temperature of the example. The characteristics of the target and the results of the sputtering are as described in the table. The amounts of the particles of Comparative Example 1 and Comparative Example 2 were slightly smaller than those of the examples.

S· 17 201109458 was added, and although it was slightly, abnormal discharge occurred in the film formation. From this result, it is understood that if the oxygen content is increased beyond the range of the present invention, the particle and discharge state are deteriorated. (Comparative Example 3 to Comparative Example 5) Although the target was produced under substantially the same conditions as in Comparative Examples 1 and 2, the amount of oxygen was further increased to 45 〇 ppm as compared with Comparative Examples 1 to 2. Further, Comparative Example 3 is a hot pressing temperature of 700 ° C, a cooling rate 2 after hot pressing, < t /min, and Comparative Example 4 is a hot pressing temperature of 65 (TC, cooling rate after hot pressing 4 t: /min, and further Comparative Example) 5 is a hot pressing temperature of 750. (:, cooling rate rc/min after hot pressing, to make the average particle size slightly larger and the X-ray intensity ratio is large, and the micro phase is confirmed. The characteristics of the target and the result of sputtering In Comparative Example 3, although the abnormal discharge was small, the amount of particles was slightly larger. In Comparative Example 4 and Comparative Example 5, the amount of particles was further increased, and the abnormal discharge was also increased. (Comparative Example 6 to Comparative Example 8) Although the dryness was produced under substantially the same conditions as in Comparative Examples 3 to 5, the second year was further increased in gas volume compared with the second comparative example 5. Comparative Example 6 and comparison The amount of oxygen of 歹1 7 is 47〇ppm, and the amount of oxygen of Comparative Example 8 is ppm. The characteristics of (10) are shown in Table i. The amount of particles in Comparative Heart to Comparative Example 8 increases, and the abnormal discharge zone The influence of the above was increased by the increase of the amount of rolling (Comparative Example 9 to Comparative Example 10) in comparison with the comparative example, which was further increased by 3 to 5 The oxygen content of Comparative Example 9 was '600 ppm with respect to Comparative Examples 3 to 5, and the oxygen amount of Comparative Example 1〇18 201109458 was 1 300 ppm. The characteristics of the target and the sputtering results are shown in Table 比较. Comparative Example 9 The amount of the particles in the comparative example 10 was further increased, and the abnormal discharge was also large. This is considered to be an effect of an increase in the amount of oxygen. (Comparative Example 11 to Comparative Example 1 3) The amount of oxygen was reduced as compared with Comparative Examples 3 to 5. However, the average crystal grain size is large, and the X-ray intensity ratio is as high as 4.6 to 110. Comparative Example u and Comparative Example 12 have less abnormal discharge, but Comparative Example 比较~Comparative Example 皆3 are all particles up to ι 5 to 21 From the above, it was confirmed that the increase in the average crystal grain size and the increase in the X-ray intensity ratio also affected the increase in the abnormal discharge. (Comparative Example 14 to Comparative Example 16) Cu_Ga dry was produced by the dazzle method. Cu was weighed and (5) The raw materials were placed at a predetermined concentration and placed in a carbon-based atmosphere, and supplied to an aerobic furnace in an argon atmosphere. Comparative Example 14 α 1〇〇〇t, Comparative Example 12, and Comparative Example 13 were higher than the respective materials. The refining point is about .c. After the material is made, it is cooled and cooled at a cooling rate of about $^111. After evaluating the characteristics of the taken product, the film was subjected to a sputtering target to perform a film formation evaluation. The results are shown in the table. As a result, it can be seen that although the oxygen content can be greatly reduced, the average crystal grain size is as high as 11 〇. 〇~83〇(4). The X-ray intensity is increased by the staff. The relative density of the comparative example 16 is also lower than the condition of the present invention. The result is 'the number of particles is changed. The number of particles is increased. Therefore, when the average particle diameter is large, the X-ray intensity ratio is larger than that of the particles, and the discharge state is improved. 201109458 (Comparative Example 17 to Comparative Example 18) The conditions are substantially the same as those of Comparative Examples 3 to 5, However, only the phase shift density is lower than the present invention, and the conditions of the present invention are not satisfied. Comparative Example 17 saw that more holes were produced. Further, in Comparative Example 18, shrinkage cavities were observed. These all have an impact on density reduction. As a result, the amounts of the particles of Comparative Example 17 to Comparative Example 1 were further increased, and the abnormal discharge was also increased. From the above, it can be understood that the decrease in relative density adversely affects the amount of particles and abnormal discharge. In the above examples, the Ga concentration was in the range of 30. 〇 to 42.6 at%, and the effects of relative density, average crystal grain size, and oxygen content were confirmed.

The same tendency is exhibited in the sintered body of the Cu-Ga alloy powder having a Ga concentration of 20 to 60 at% and a balance of Cu and unavoidable impurities. Therefore, the present invention is all applicable to a sintered body of a Cu_Ga alloy powder having a concentration of 2 〇 to 6 〇 at% and a residual portion of Cu and an unavoidable impurity, as long as it is a technical field to which the present invention pertains. Those with ordinary knowledge are easy to understand. (Availability of the pedestal) According to the present invention, it is possible to supply a Cu-Ga sintered body sputtering target in a wide-area, bismuth-supplied seed, and to form a segregation and a long time of reducing the Su and then discharging. The film obtained by sputtering is hardly produced; the Cii-〇a sintered body target of the raw particles and the manufacture thereof, so that the Cu_Ga film can be produced by using the target, especially for the CIGS system used as the selenization method. Destruction;, is the material for the manufacture of too much battery. [Simple description of the diagram] No 20 201109458 [Main component symbol description benefits

Claims (1)

201109458 VII. Patent application scope: 1. A Cu-Ga alloy sintered body sputtering target, characterized in that it is a Cu_Ga alloy powder with a Ga concentration of 2〇~6〇at% and the remainder being a avoided impurity. The sintered body is composed of a sintered body having a relative density of 97% or more, an average crystal grain size of 5 to 3 () "claw, and a good person 1 of 4 〇〇 ppm or less. Gas 芑 2. Such as Shen. The Cu-Ga alloy sintered body of the i-item is composed of a single composition. The Cu-Ga alloy is composed of a single composition. 3 is as in the first or second patent application scope, and the alloy sintered body is also dry. The intensity of the peak other than the main peak of the X-ray diffraction of the Ga alloy is 5% or less with respect to the intensity of the main peak. Further, the Cu-Ga alloy is fired, ', α as in any one of the items 1 to 3 of the patent application. a body sputtering target, wherein the Cu-Ga alloy composition is substantially a γ phase or a main phase is a 7* phase. 5. A method for manufacturing a Cu-Ga alloy sintered body sputtering target, which is to use a Cii and Ga raw material. After melting and cooling, the pulverized /tD S raw material powder is formed into a Cu-Ga alloy sputtering target by a hot pressing method. Depending on: The temperature at which the hot pressing is maintained is set to be 50 to 200 C lower than the melting point of the mixed raw material powder. The holding time is set to 1 to 3 hours, and the cooling rate is set to 5 t / min or more. Hot pressing is performed for 3 〇 to 4 〇 MPa. 6. A method for producing a Cu-Ga alloy sintered body sputtering target, which is obtained by melting and cooling Cu and Ga raw materials, and then pulverizing by hot pressing. The mixed raw material powder is produced as a method of the 201109458 Cu-Ga alloy sintered body sputtering target according to any one of claims 1 to 4, characterized in that: the holding temperature during hot pressing is determined as a mixed raw material powder. The melting point is low ~ 200 C, the holding time is set to 1~3 j, pull, 'people, and soil. The threshold of Feng Wei's cold part is set to 5. (: / min or more 'addition of mixed raw material powder The pressing pressure is set to 3〇~4〇Mpa for hot pressing. '',, 7. For the manufacturing method of Cu_G# gold sintered body splashing coarse according to the 5th or 6th patent of the patent application' (4) gas atomization method or The water atomization method is used to carry out the melting of the Ga raw material and the pulverization after cooling. 8. A light absorbing layer, It is prepared by plating a Cu-G a alloy sintered body machine according to any one of the scopes of the patent application. 9. A CIGS-based solar cell, a basin injury, you have a patent application scope 8 Light absorbing layer. 8. Pattern: (none)