JP2013184866A - Method for producing czts compound semiconductor - Google Patents
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Abstract
Description
本発明は、ＣＺＴＳ化合物半導体の製造方法に関する。 The present invention relates to a method for producing a CZTS compound semiconductor.
太陽電池は、発電量当たりの二酸化炭素排出量が少なく、発電用の燃料が不要であるため、地球温暖化防止等に寄与することが期待されている。現在、実用化されている太陽電池の中では、単結晶シリコン又は多結晶シリコンを用いた、一組のｐｎ接合を有する単接合太陽電池が主流となっている。このほか、近年では、シリコンに依存しない薄膜太陽電池等についても、盛んに研究開発が進められている。 Solar cells are expected to contribute to the prevention of global warming and the like because they emit less carbon dioxide per power generation and do not require fuel for power generation. Currently, single-junction solar cells having a pair of pn junctions using single-crystal silicon or polycrystalline silicon are the mainstream among solar cells in practical use. In addition, in recent years, research and development has been actively conducted on thin-film solar cells that do not depend on silicon.
ＣＺＴＳ系薄膜太陽電池は、シリコンの代わりにＣｕ、Ｚｎ、Ｓｎ、及び、Ｓを用いた化合物半導体（以下において、「ＣＺＴＳ」又は「ＣＺＴＳ化合物半導体」という。）を、光吸収層に使用する薄膜太陽電池である。これらの物質は入手しやすく安価であるため、ＣＺＴＳ系薄膜太陽電池が注目されている。 A CZTS thin film solar cell is a thin film that uses a compound semiconductor (hereinafter referred to as “CZTS” or “CZTS compound semiconductor”) using Cu, Zn, Sn, and S instead of silicon as a light absorption layer. It is a solar cell. Since these materials are easily available and inexpensive, CZTS thin film solar cells have attracted attention.
ＣＺＴＳ系薄膜太陽電池に関する技術として、例えば特許文献１には、第二硫化銅、硫化亜鉛、及び、硫化錫の粉体を混合した後、ホットプレス法にて１０ＭＰａ以上かつ７００℃以上で１時間以上に亘って焼成する、硫化物焼結体ターゲットの製造方法が開示されている。 As a technique related to the CZTS-based thin film solar cell, for example, in Patent Document 1, after mixing powders of cupric sulfide, zinc sulfide, and tin sulfide, hot pressing is performed at 10 MPa or more and 700 ° C. or more for 1 hour. The manufacturing method of the sulfide sintered compact target baked over the above is disclosed.
特許文献１に７００℃以上の温度で焼成する製造方法が開示されているように、これまで、緻密なＣＺＴＳを製造するためには、６７５℃以上の温度で焼成する必要があった。ここで、ＣＺＴＳを太陽電池に用いる場合、電極の表面にＣＺＴＳを形成する形態が想定され、緻密なＣＺＴＳを形成するために、電極の表面に形成したＣＺＴＳを６７５℃以上の温度で焼成することが考えられる。しかしながら、例えば、電極としてＭｏ電極を使用する場合、温度が５７０℃以上になると、ＣＺＴＳ及びＭｏの界面で反応が進行して異相が形成される。そのため、６７５℃以上の高温で焼成する過程を経てＣＺＴＳ系薄膜太陽電池を作製しても、本来の材料特性を示さず、性能を向上させることは困難であった。 As disclosed in Patent Document 1, a manufacturing method in which baking is performed at a temperature of 700 ° C. or higher, so far, it has been necessary to perform baking at a temperature of 675 ° C. or higher in order to manufacture a dense CZTS. Here, when CZTS is used for a solar cell, it is assumed that CZTS is formed on the surface of the electrode, and in order to form dense CZTS, CZTS formed on the surface of the electrode is fired at a temperature of 675 ° C. or higher. Can be considered. However, for example, when a Mo electrode is used as the electrode, when the temperature becomes 570 ° C. or higher, the reaction proceeds at the interface between CZTS and Mo and a heterogeneous phase is formed. Therefore, even if a CZTS thin film solar cell is manufactured through a process of baking at a high temperature of 675 ° C. or higher, it does not show the original material properties and it is difficult to improve the performance.
そこで本発明は、緻密なＣＺＴＳ化合物半導体を従来よりも低い焼成温度で製造することが可能な、ＣＺＴＳ化合物半導体の製造方法を提供することを課題とする。 Then, this invention makes it a subject to provide the manufacturing method of the CZTS compound semiconductor which can manufacture a precise | minute CZTS compound semiconductor at the firing temperature lower than before.
本発明者らは、鋭意検討の結果、焼結助剤（ＳｎＳ又はＳｎＳ２）を添加して焼成することにより、従来よりも低い温度で焼成しても緻密なＣＺＴＳ化合物半導体を製造することが可能になることを知見した。本発明は、かかる知見に基づいて完成させた。 As a result of intensive studies, the inventors of the present invention can produce a dense CZTS compound semiconductor by adding a sintering aid (SnS or SnS 2 ) and firing, even if firing at a lower temperature than conventional. I knew that it would be possible. The present invention has been completed based on this finding.
上記課題を解決するために、本発明は以下の手段をとる。すなわち、
本発明の第１の態様は、焼結助剤が存在する環境下において、Ｃｕ、Ｚｎ、Ｓｎ、及び、Ｓを含有する被焼結体を焼成する工程を有し、焼結助剤にＳｎＳが含まれる、ＣＺＴＳ化合物半導体の製造方法である。
In order to solve the above problems, the present invention takes the following means. That is,
1st aspect of this invention has the process of baking the to-be-sintered body containing Cu, Zn, Sn, and S in the environment where a sintering auxiliary agent exists, SnS is used as a sintering auxiliary agent. Is a method for producing a CZTS compound semiconductor.
ここに、本発明の第１の態様及び以下に示す本発明の他の態様において、「Ｃｕ、Ｚｎ、Ｓｎ、及び、Ｓを含有する被焼結体」とは、焼成されることによって緻密化したＣＺＴＳ化合物半導体になる物質をいう。例えば、スパッタ法や真空蒸着法等の真空法によって形成した、硫化工程を経る前の前駆体膜のほか、いわゆる固相合成法や液相から合成したＣＺＴＳ化合物半導体等が、「Ｃｕ、Ｚｎ、Ｓｎ、及び、Ｓを含有する被焼結体」に含まれ得る。ＳｎＳを添加してＣＺＴＳを焼成することにより、例えば５６０℃で焼成しても、相対密度が９５％以上であるＣＺＴＳを製造することが可能になる。したがって、本発明の第１の態様によれば、緻密なＣＺＴＳ化合物半導体を従来よりも低い焼成温度で製造することが可能な、ＣＺＴＳ化合物半導体の製造方法を提供することができる。 Here, in the first aspect of the present invention and the other aspects of the present invention described below, “a sintered body containing Cu, Zn, Sn, and S” is densified by firing. A substance that becomes a CZTS compound semiconductor. For example, in addition to a precursor film formed by a vacuum method such as a sputtering method or a vacuum deposition method and before passing through a sulfidation step, a so-called solid phase synthesis method or a CZTS compound semiconductor synthesized from a liquid phase includes “Cu, Zn, It can be included in “sintered body containing Sn and S”. By firing Sn with the addition of CZTS, it becomes possible to produce CZTS having a relative density of 95% or higher even when fired at 560 ° C., for example. Therefore, according to the first aspect of the present invention, it is possible to provide a method for producing a CZTS compound semiconductor capable of producing a dense CZTS compound semiconductor at a firing temperature lower than conventional.
本発明の第２の態様は、焼結助剤が存在する環境下において、Ｃｕ、Ｚｎ、Ｓｎ、及び、Ｓを含有する被焼結体を焼成する工程を有し、焼結助剤にＳｎＳ２が含まれる、ＣＺＴＳ化合物半導体の製造方法である。 The second aspect of the present invention includes a step of firing a sintered body containing Cu, Zn, Sn, and S in an environment in which a sintering aid is present, and the sintering aid contains SnS. 2 is a method for producing a CZTS compound semiconductor.
ＳｎＳ２を添加してＣＺＴＳを焼成することにより、例えば５６０℃で焼成しても、相対密度が８０％以上であるＣＺＴＳを製造することが可能になる。したがって、本発明の第２の態様によれば、緻密なＣＺＴＳ化合物半導体を従来よりも低い焼成温度で製造することが可能な、ＣＺＴＳ化合物半導体の製造方法を提供することができる。 When CZTS is fired by adding SnS 2 , it becomes possible to produce CZTS having a relative density of 80% or more even when fired at 560 ° C., for example. Therefore, according to the second aspect of the present invention, it is possible to provide a method for producing a CZTS compound semiconductor capable of producing a dense CZTS compound semiconductor at a lower firing temperature than in the past.
また、上記本発明の第１の態様、及び、上記本発明の第２の態様において、被焼結体の質量をＸ、焼結助剤の質量をＹとするとき、０．０１≦Ｙ／Ｘ≦０．１であることが好ましい。かかる形態とすることにより、相対密度を高めたＣＺＴＳ化合物半導体を製造しやすくなる。 In the first aspect of the present invention and the second aspect of the present invention, when the mass of the object to be sintered is X and the mass of the sintering aid is Y, 0.01 ≦ Y / It is preferable that X ≦ 0.1. By setting it as this form, it becomes easy to manufacture the CZTS compound semiconductor which raised the relative density.
本発明によれば、緻密なＣＺＴＳ化合物半導体を従来よりも低い焼成温度で製造することが可能な、ＣＺＴＳ型化合物半導体の製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the CZTS type compound semiconductor which can manufacture a precise | minute CZTS compound semiconductor at a calcination temperature lower than before can be provided.
以下、図面を参照しつつ、本発明のＣＺＴＳ化合物半導体の製造方法（以下において、「本発明の製造方法」ということがある。）について説明する。なお、以下に示す形態は例示であり、本発明の製造方法は以下に示す形態に限定されない。 Hereinafter, a method for producing a CZTS compound semiconductor of the present invention (hereinafter, also referred to as “manufacturing method of the present invention”) will be described with reference to the drawings. In addition, the form shown below is an illustration and the manufacturing method of this invention is not limited to the form shown below.
図１は、本発明のＣＺＴＳ化合物半導体の製造方法を説明する図である。図１に示した本発明の製造方法は、被焼結体作製工程（Ｓ１）と、焼成工程（Ｓ２）と、を有している。 FIG. 1 is a diagram for explaining a method for producing a CZTS compound semiconductor of the present invention. The manufacturing method of the present invention shown in FIG. 1 includes a sintered body manufacturing step (S1) and a firing step (S2).
被焼結体作製工程は、後述する焼成工程で焼成されて緻密化される被焼結体を作製する工程である。被焼結体作製工程は、被焼結体を作製可能であれば、その形態は特に限定されない。被焼結体作製工程は、例えば、Ｃｕ−Ｚｎ−Ｓｎ−Ｓ前駆体膜を、スパッタ法や真空蒸着法等の真空法によって形成する形態であっても良く、いわゆる固相合成法や、液相からＣＺＴＳ粒子を合成する水熱合成法、有機溶剤法、ゾルゲル法、めっき法等によって、ＣＺＴＳ化合物半導体を作製する形態であっても良い。 A to-be-sintered body preparation process is a process of producing the to-be-sintered body baked and densified by the baking process mentioned later. As long as a to-be-sintered body preparation process can produce a to-be-sintered body, the form will not be specifically limited. The to-be-sintered body production | generation process may be a form which forms a Cu-Zn-Sn-S precursor film | membrane by vacuum methods, such as a sputtering method and a vacuum evaporation method, for example, what is called a solid-phase synthesis method, liquid A form in which a CZTS compound semiconductor is produced by a hydrothermal synthesis method of synthesizing CZTS particles from a phase, an organic solvent method, a sol-gel method, a plating method, or the like may be used.
焼成工程は、被焼結体作製工程で作製した被焼結体を、焼結助剤が存在する環境下で焼成することにより、緻密化されたＣＺＴＳを作製する工程である。焼成工程で使用可能な焼結助剤としては、ＳｎＳやＳｎＳ２を例示することができる。例えば、被焼結体作製工程がスパッタ法や真空蒸着法等の真空法により前駆体を形成する形態である場合、焼成工程は、前駆体に、スパッタや蒸着等によってＳｎＳやＳｎＳ２を過剰に供給した後、硫化水素による硫化及び焼成によって、緻密化されたＣＺＴＳを作製する工程、とすることができる。本発明において、焼成工程で使用する焼結助剤の使用量は特に限定されないが、相対密度の高い緻密なＣＺＴＳ化合物半導体を製造しやすい形態にする観点から、Ｃｕ２ＺｎＳｎＳ４の質量をＸ、焼結助剤の質量をＹとするとき、０．０１≦Ｙ／Ｘ≦０．１とすることが好ましく、０．０２≦Ｙ／Ｘ≦０．０４とすることがより好ましい。 The firing step is a step of producing a densified CZTS by firing the sintered body produced in the sintered body production step in an environment where a sintering aid is present. The sintering aid can be used in the baking step, it can be exemplified SnS and SnS 2. For example, when the sintered body manufacturing process is a form in which the precursor is formed by a vacuum method such as a sputtering method or a vacuum deposition method, the firing process is performed by adding excessive SnS or SnS 2 to the precursor by sputtering or deposition. After the supply, a step of producing a densified CZTS by sulfidation and baking with hydrogen sulfide can be performed. In the present invention, the amount of the sintering aid used in the firing step is not particularly limited, but from the viewpoint of making a dense CZTS compound semiconductor with a high relative density easy to manufacture, the mass of Cu 2 ZnSnS 4 is X, When the mass of the sintering aid is Y, 0.01 ≦ Y / X ≦ 0.1 is preferable, and 0.02 ≦ Y / X ≦ 0.04 is more preferable.
焼成工程を有する本発明の製造方法によれば、従来は６７５℃以上であった焼成温度を、例えば５６０℃にまで低下させても、相対密度が８０％以上であるＣＺＴＳ化合物半導体を製造することが可能になる。すなわち、本発明によれば、Ｍｏの表面に形成したＣＺＴＳを、ＣＺＴＳとＭｏとが反応しない温度で焼成しても、ＣＺＴＳを緻密化することができる。したがって、ＣＺＴＳ系薄膜太陽電池を製造する際に、本発明の製造方法によって緻密化したＣＺＴＳを製造することにより、変換効率を高めたＣＺＴＳ系薄膜太陽電池を製造することが可能になる。 According to the production method of the present invention having a firing step, a CZTS compound semiconductor having a relative density of 80% or more even when the firing temperature, which was 675 ° C. or higher in the past, is reduced to, for example, 560 ° C. Is possible. That is, according to the present invention, even if CZTS formed on the surface of Mo is fired at a temperature at which CZTS and Mo do not react, CZTS can be densified. Therefore, when manufacturing a CZTS-based thin film solar cell, it is possible to manufacture a CZTS-based thin film solar cell with improved conversion efficiency by manufacturing a dense CZTS by the manufacturing method of the present invention.
また、本発明の製造方法では、ＣＺＴＳ化合物半導体を構成する元素によって構成された化合物を焼結助剤として用いている。そのため、添加した焼結助剤は、焼結後に固溶してカルコパイライト単相になり、異相は形成されない。したがって、本発明で製造したＣＺＴＳ化合物半導体を用いることにより、太陽電池の変換効率を高めやすくなる。 Moreover, in the manufacturing method of this invention, the compound comprised by the element which comprises a CZTS compound semiconductor is used as a sintering auxiliary agent. For this reason, the added sintering aid is dissolved into a chalcopyrite single phase after sintering, and no heterogeneous phase is formed. Therefore, it becomes easy to improve the conversion efficiency of a solar cell by using the CZTS compound semiconductor manufactured by this invention.
＜実施例１＞
Ｃｕ２ＺｎＳｎＳ４及び焼結助剤の質量比が、Ｃｕ２ＺｎＳｎＳ４：焼結助剤＝１００：３となるように、焼結助剤（Ｃｕ２Ｓ、ＺｎＳ、ＳｎＳ、及び、ＳｎＳ２の各粉末）を計量した。そして、Ｃｕ２ＺｎＳｎＳ４のみ、又は、Ｃｕ２ＺｎＳｎＳ４及び焼結助剤をボールミルに投入して乾式で２４時間に亘って混合することにより、混合粉末を得た。その後、得られた混合粉末を直径１０ｍｍ程度のディスク状に成形し、さらに圧力２４５ＭＰａで冷間等方圧成形（ＣＩＰ成形）することにより、焼結用圧粉体を得た。そして、得られた焼結用圧粉体を、窒素雰囲気中で、焼成温度６７５℃又は５６０℃で２時間に亘って焼成した後、取り出した試料の相対密度を測定した。結果を図２に示す。また、焼成温度を５６０℃にした場合の結果を表１に示す。
<Example 1>
Sintering aids (Cu 2 S, ZnS, SnS, and SnS 2 so that the mass ratio of Cu 2 ZnSnS 4 and the sintering aid is Cu 2 ZnSnS 4 : sintering aid = 100: 3. Each powder) was weighed. Then, Cu 2 ZnSnS 4 alone or Cu 2 ZnSnS 4 and a sintering aid were charged into a ball mill and mixed for 24 hours in a dry manner to obtain a mixed powder. Thereafter, the obtained mixed powder was formed into a disk shape having a diameter of about 10 mm and further subjected to cold isostatic pressing (CIP molding) at a pressure of 245 MPa to obtain a green compact for sintering. The obtained green compact for sintering was fired in a nitrogen atmosphere at a firing temperature of 675 ° C. or 560 ° C. for 2 hours, and then the relative density of the sample taken out was measured. The results are shown in FIG. Table 1 shows the results when the firing temperature was set to 560 ° C.
図２に示したように、焼成温度が６７５℃の場合、焼結助剤を添加しない試料では、相対密度が９７％程度のＣＺＴＳ化合物半導体が得られた。また、焼結助剤としてＣｕ２Ｓ、ＺｎＳ、及び、ＳｎＳ２からなる群より選択した１種を添加した試料では、相対密度が８５％程度のＣＺＴＳ化合物半導体が得られ、焼結助剤としてＳｎＳを添加した試料では、相対密度が９８％以上のＣＺＴＳ化合物半導体が得られた。 As shown in FIG. 2, when the firing temperature was 675 ° C., a CZTS compound semiconductor having a relative density of about 97% was obtained in the sample to which the sintering aid was not added. In addition, in the sample added with one kind selected from the group consisting of Cu 2 S, ZnS, and SnS 2 as a sintering aid, a CZTS compound semiconductor having a relative density of about 85% is obtained. In the sample to which SnS was added, a CZTS compound semiconductor having a relative density of 98% or more was obtained.
一方、焼成温度が５６０℃の場合、焼結助剤を添加しない試料、及び、焼結助剤としてＣｕ２Ｓ又はＺｎＳを添加した試料では、相対密度が７０％程度（最低で６７．８％、最高で７０．３％）のＣＺＴＳ化合物半導体が得られた。これに対し、焼成温度が５６０℃の場合、焼結助剤としてＳｎＳを添加した試料では、相対密度が９５％程度（最低で９４．７％、最高で９５．８％）のＣＺＴＳ化合物半導体が得られ、焼結助剤としてＳｎＳ２を添加した試料では、相対密度が７０％よりも高い（最低で７３．９％、最高で８０．４％）のＣＺＴＳ化合物半導体が得られた。以上の結果から、焼結助剤としてＳｎＳやＳｎＳ２を用いることにより、焼成温度を低減しても緻密化されたＣＺＴＳ化合物半導体を製造可能であることが確認された。 On the other hand, when the firing temperature is 560 ° C., the relative density is about 70% (at least 67.8%) in the sample without adding the sintering aid and the sample with Cu 2 S or ZnS added as the sintering aid. , A maximum of 70.3%) CZTS compound semiconductor was obtained. On the other hand, when the firing temperature is 560 ° C., the CZTS compound semiconductor having a relative density of about 95% (minimum 94.7%, maximum 95.8%) in the sample added with SnS as a sintering aid. In the sample obtained by adding SnS 2 as a sintering aid, a CZTS compound semiconductor having a relative density higher than 70% (minimum 73.9%, maximum 80.4%) was obtained. From the above results, it was confirmed that by using SnS or SnS 2 as a sintering aid, a densified CZTS compound semiconductor can be manufactured even if the firing temperature is reduced.
＜実施例２＞
Ｃｕ２ＺｎＳｎＳ４及びＳｎＳの質量比が、Ｃｕ２ＺｎＳｎＳ４：ＳｎＳ＝１００：１以上１３以下となるように、ＳｎＳ粉末を計量した。そして、Ｃｕ２ＺｎＳｎＳ４のみ、又は、Ｃｕ２ＺｎＳｎＳ４及びＳｎＳをボールミルに投入して乾式で２４時間に亘って混合することにより、混合粉末を得た。その後、得られた混合粉末を直径１０ｍｍ程度のディスク状に成形し、さらに圧力２４５ＭＰａで冷間等方圧成形（ＣＩＰ成形）することにより、焼結用圧粉体を得た。そして、得られた焼結用圧粉体を、窒素雰囲気中で、焼成温度５６０℃で２時間に亘って焼成した後、取り出した試料の相対密度を測定した。結果を図３に示す。図３の縦軸は相対密度、横軸はＳｎＳの添加量である。また、ＳｎＳを添加しなかった場合、Ｃｕ２ＺｎＳｎＳ４に対して１質量％のＳｎＳを添加した場合、Ｃｕ２ＺｎＳｎＳ４に対して３質量％のＳｎＳを添加した場合、及び、Ｃｕ２ＺｎＳｎＳ４に対して５質量％のＳｎＳを添加した場合の結果を、表２に示す。また、ＳｎＳを添加しなかった場合、Ｃｕ２ＺｎＳｎＳ４に対して１質量％のＳｎＳを添加した場合、Ｃｕ２ＺｎＳｎＳ４に対して３質量％のＳｎＳを添加した場合、及び、Ｃｕ２ＺｎＳｎＳ４に対して５質量％のＳｎＳを添加した場合の焼成表面の電子顕微鏡写真を図４に示す。
<Example 2>
The SnS powder was weighed so that the mass ratio of Cu 2 ZnSnS 4 and SnS was Cu 2 ZnSnS 4 : SnS = 100: 1 or more and 13 or less. Then, only Cu 2 ZnSnS 4 or Cu 2 ZnSnS 4 and SnS were charged into a ball mill and mixed for 24 hours in a dry manner to obtain a mixed powder. Thereafter, the obtained mixed powder was formed into a disk shape having a diameter of about 10 mm and further subjected to cold isostatic pressing (CIP molding) at a pressure of 245 MPa to obtain a green compact for sintering. The obtained green compact for sintering was fired in a nitrogen atmosphere at a firing temperature of 560 ° C. for 2 hours, and then the relative density of the sample taken out was measured. The results are shown in FIG. In FIG. 3, the vertical axis represents the relative density, and the horizontal axis represents the amount of SnS added. Also, when not added SnS, if the addition of 1 wt% of SnS respect Cu 2 ZnSnS 4, the case of adding SnS 3 wt% relative to Cu 2 ZnSnS 4, and, Cu 2 ZnSnS 4 Table 2 shows the results when 5% by mass of SnS was added. Also, when not added SnS, if the addition of 1 wt% of SnS respect Cu 2 ZnSnS 4, the case of adding SnS 3 wt% relative to Cu 2 ZnSnS 4, and, Cu 2 ZnSnS 4 FIG. 4 shows an electron micrograph of the fired surface when 5% by mass of SnS is added.
図３及び表２に示したように、ＳｎＳを添加せずに焼成する過程を経て製造したＣＺＴＳ化合物半導体は、相対密度が７０％程度（最低で６７．８％、最高で７０．３％）であったが、Ｃｕ２ＺｎＳｎＳ４に対して１質量％以上のＳｎＳ（焼結助剤）を添加して焼成することにより、相対密度を高めたＣＺＴＳ化合物半導体を製造することができた。今回の実験では、Ｃｕ２ＺｎＳｎＳ４に対して３質量％のＳｎＳを添加して焼成する過程を経て製造したＣＺＴＳ化合物半導体の相対密度が最も高かった。 As shown in FIG. 3 and Table 2, the CZTS compound semiconductor manufactured through the process of firing without adding SnS has a relative density of about 70% (minimum 67.8%, maximum 70.3%). However, by adding 1% by mass or more of SnS (sintering aid) to Cu 2 ZnSnS 4 and firing, a CZTS compound semiconductor with an increased relative density could be produced. In this experiment, the relative density of the CZTS compound semiconductor produced through the process of adding 3% by mass of SnS to Cu 2 ZnSnS 4 and firing was the highest.
＜実施例３＞
Ｃｕ２ＺｎＳｎＳ４及びＳｎＳの質量比が、Ｃｕ２ＺｎＳｎＳ４：ＳｎＳ＝１００：３となるように、ＳｎＳ粉末を計量した。そして、Ｃｕ２ＺｎＳｎＳ４のみ、又は、Ｃｕ２ＺｎＳｎＳ４及びＳｎＳをボールミルに投入して乾式で２４時間に亘って混合することにより、混合粉末を得た。その後、得られた混合粉末を直径１０ｍｍ程度のディスク状に成形し、さらに圧力２４５ＭＰａで冷間等方圧成形（ＣＩＰ成形）することにより、焼結用圧粉体を得た。そして、得られた焼結用圧粉体を、窒素雰囲気中で、焼成温度５００℃、５６０℃、又は、６７５℃で２時間に亘って焼成した後、取り出した試料の相対密度を測定した。結果を図５及び表３に示す。図５の縦軸は相対密度、横軸は焼成温度である。
<Example 3>
The SnS powder was weighed so that the mass ratio of Cu 2 ZnSnS 4 and SnS was Cu 2 ZnSnS 4 : SnS = 100: 3. Then, only Cu 2 ZnSnS 4 or Cu 2 ZnSnS 4 and SnS were charged into a ball mill and mixed for 24 hours in a dry manner to obtain a mixed powder. Thereafter, the obtained mixed powder was formed into a disk shape having a diameter of about 10 mm and further subjected to cold isostatic pressing (CIP molding) at a pressure of 245 MPa to obtain a green compact for sintering. The obtained green compact for sintering was fired at a firing temperature of 500 ° C., 560 ° C., or 675 ° C. for 2 hours in a nitrogen atmosphere, and then the relative density of the sample taken out was measured. The results are shown in FIG. The vertical axis in FIG. 5 is the relative density, and the horizontal axis is the firing temperature.
図５及び表３に示したように、ＳｎＳを添加せずに焼成する過程を経て製造したＣＺＴＳ化合物半導体は、焼成温度を５００℃にした場合の相対密度が６９．１％、焼成温度を５６０℃にした場合の相対密度が６８．８％であり、焼成温度を６７５℃にした場合の相対密度は９６．８％であった。すなわち、ＳｎＳを添加せずに焼成する場合には、焼成温度を５６０℃にしても相対密度を高めることはできなかった。 As shown in FIG. 5 and Table 3, the CZTS compound semiconductor manufactured through the process of firing without adding SnS has a relative density of 69.1% when the firing temperature is 500 ° C., and the firing temperature is 560. The relative density at 6 ° C. was 68.8%, and the relative density at 675 ° C. was 96.8%. That is, when firing without adding SnS, the relative density could not be increased even if the firing temperature was 560 ° C.
一方、Ｃｕ２ＺｎＳｎＳ４に対して３質量％のＳｎＳを添加して焼成する過程を経て製造したＣＺＴＳ化合物半導体は、焼成温度を５００℃にした場合の相対密度が６９．６％であり、焼成温度を５６０℃にした場合の相対密度は９５．３％、焼成温度を６７５℃にした場合の相対密度は９９．５％であった。すなわち、ＳｎＳを添加して焼成することにより、緻密なＣＺＴＳ化合物半導体が得られる焼成温度を、ＳｎＳを添加せずに焼成した場合の６７５℃から５６０℃へと１１５℃低減することができた。 On the other hand, the CZTS compound semiconductor manufactured through the process of adding 3% by mass of SnS to Cu 2 ZnSnS 4 and baking it has a relative density of 69.6% when the baking temperature is 500 ° C. The relative density when the temperature was 560 ° C. was 95.3%, and the relative density when the firing temperature was 675 ° C. was 99.5%. That is, by adding SnS and firing, the firing temperature at which a dense CZTS compound semiconductor is obtained could be reduced by 115 ° C. from 675 ° C. when firing without adding SnS to 560 ° C.
また、焼成後の生成層をＸ線回折により調査した結果を図６及び表４に示す。図６の縦軸は回折強度であり、横軸は回折角２θである。図６に示した４つの結果のうち、一番上はＳｎＳを添加して５６０℃で焼成した場合の結果であり、上から二番目はＳｎＳを添加せずに５６０℃で焼成した場合の結果であり、上から三番目はＳｎＳを添加して６７５℃で焼成した場合の結果であり、一番下はＳｎＳを添加せずに６７５℃で焼成した場合の結果である。また、表４における強度比は、Ｃｕ２ＺｎＳｎＳ４のＸ線回折強度に対するＳｎＯ２のＸ線回折強度の比である。 Moreover, the result of having investigated the production | generation layer after baking by X-ray diffraction is shown in FIG. The vertical axis in FIG. 6 is the diffraction intensity, and the horizontal axis is the diffraction angle 2θ. Among the four results shown in FIG. 6, the top is the result when SnS is added and baked at 560 ° C., and the second from the top is the result when baked at 560 ° C. without adding SnS. The third from the top is the result when SnS is added and baked at 675 ° C., and the bottom is the result when baked at 675 ° C. without adding SnS. The intensity ratio in Table 4 is the ratio of the X-ray diffraction intensity of SnO 2 to the X-ray diffraction intensity of Cu 2 ZnSnS 4 .
図６及び表４に示したように、ＳｎＳを添加して６７５℃で焼成した場合には、過剰となったＳｎＯ２が不純物として生成した。これに対し、ＳｎＳを添加して５６０℃で焼成した場合には、ＳｎＳを添加せずに焼成した場合と同様に、不純物（ＳｎＯ２）は生成されないことが示された。 As shown in FIG. 6 and Table 4, when SnS was added and baked at 675 ° C., excess SnO 2 was generated as an impurity. On the other hand, it was shown that when SnS was added and baked at 560 ° C., no impurities (SnO 2 ) were generated as in the case of baking without adding SnS.
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