JP2019178012A - N-type SnS semiconductor and solar cell using the same - Google Patents
N-type SnS semiconductor and solar cell using the same Download PDFInfo
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 46
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 abstract description 18
- 229910052736 halogen Inorganic materials 0.000 abstract description 9
- 150000002367 halogens Chemical class 0.000 abstract description 9
- 231100000701 toxic element Toxicity 0.000 abstract description 4
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 6
- 239000011630 iodine Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000002490 spark plasma sintering Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- -1 CIGS systems Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
Abstract
Description
本発明は、ＳｎＳ（硫化スズ）半導体に関し、特にｎ型の電気特性を示す半導体およびそれを用いた太陽電池に関する。 The present invention relates to a SnS (tin sulfide) semiconductor, and particularly to a semiconductor exhibiting n-type electrical characteristics and a solar cell using the same.
太陽エネルギーを利用した太陽光発電は、クリーンかつ地球温暖化の防止に有望なため、将来のエネルギー源として大きく期待され、その研究開発が進められている。 Solar power generation using solar energy is promising for clean and prevention of global warming, so it is highly expected as a future energy source, and its research and development is underway.
太陽電池に使用されている半導体材料として、シリコン系半導体材料、化合物半導体材料などが挙げられる。 Examples of semiconductor materials used in solar cells include silicon-based semiconductor materials and compound semiconductor materials.
これら太陽電池向け半導体材料として、シリコン系半導体材料は２０％前後の変換効率を持つがその材料コストが高いことが問題となっている。 As a semiconductor material for these solar cells, a silicon-based semiconductor material has a conversion efficiency of about 20%, but its material cost is a problem.
また、化合物半導体系材料はＧａＡｓ、ＩｎＰに代表されるIII-V族半導体やＣＩＧＳ系やＣｄＴｅ系などが挙げられる。これらの中には多接合化や集光などの技術を組み合わせることで４０％近くにも及ぶ高い変換効率を持つ高性能の材料もあるが概ね高コストであり、主に宇宙用として使われている。また、ＣＩＧＳ、ＣｄＴｅ、ＧａＡｓなどの化合物半導体の中にはＩｎやＧａといった希少元素や、ＣｄやＡｓといった有毒元素を含むものがその主流である。 Examples of compound semiconductor materials include III-V group semiconductors represented by GaAs and InP, CIGS systems, and CdTe systems. Among these, there are high-performance materials with high conversion efficiency of nearly 40% by combining technologies such as multi-junction and condensing, but they are generally expensive and are mainly used for space applications. Yes. Further, among compound semiconductors such as CIGS, CdTe, and GaAs, those containing rare elements such as In and Ga and toxic elements such as Cd and As are the mainstream.
太陽電池は、基本的にｐ型半導体とｎ型半導体とを接合したｐｎ接合により構成される。ｐｎ接合には、ｐ型半導体とｎ型半導体の両方に同じ物質を用いるホモ接合と、ｐ型半導体とｎ型半導体がそれぞれ違う物質であるヘテロ接合がある。ヘテロ接合の場合、結晶性、格子定数の違いなどから接合界面に欠陥が生じ、光吸収により生成した電子、正孔が界面欠陥によりトラップされ、再結合が生じやすくなるという問題がある。このため、もともとの材料が持つ特性を活かすことが困難である。 A solar cell is basically composed of a pn junction in which a p-type semiconductor and an n-type semiconductor are joined. The pn junction includes a homojunction that uses the same material for both the p-type semiconductor and the n-type semiconductor, and a heterojunction in which the p-type semiconductor and the n-type semiconductor are different materials. In the case of a heterojunction, there is a problem in that defects occur at the junction interface due to differences in crystallinity and lattice constant, and electrons and holes generated by light absorption are trapped by the interface defect and recombination easily occurs. For this reason, it is difficult to make use of the characteristics of the original material.
化合物半導体であるＳｎＳ（硫化スズ）は非毒性元素／非希少元素のみからなり、その電子移動度は計算値で７３５００ｃｍ２／Ｖｓ、正孔移動度が２３７００ｃｍ２／Ｖｓと他の半導体と比べて非常に大きな値を有している。また、光吸収係数も約１０4ｃｍ−１と高く、バンドギャップも約１．３５ｅＶと太陽光の吸収に最適な１．４ｅＶと近い値である。それゆえ、ＳｎＳホモ接合太陽電池が実現すれば、理論的には２０％以上の変換効率が期待される。 SnS (tin sulfide), which is a compound semiconductor, consists only of non-toxic elements / non-rare elements, and its electron mobility is 73500 cm 2 / Vs and hole mobility is 23700 cm 2 / Vs in comparison with other semiconductors. It has a very large value. In addition, the light absorption coefficient is as high as about 10 4 cm −1 and the band gap is about 1.35 eV, which is close to 1.4 eV which is optimal for absorption of sunlight. Therefore, if an SnS homojunction solar cell is realized, a conversion efficiency of 20% or more is theoretically expected.
しかしながらが、ＳｎＳのｎ型化については、非特許文献１や非特許文献２などにその報告例があるに過ぎない。非特許文献１はＳｎＳにＰｂ添加する方法によるｎ型ＳｎＳの研究報告であるが、この方法の場合ＳｎＳ１−ｘＰｂｘはｘ＞２０％でｎ型化を示すものであり、有毒のＰｂを用いるものである。一方、非特許文献２は本発明者らによるＣｌ添加したＳｎＳがｎ型伝導を示す事例である。この報告例は、ハロゲン元素をドープして作成されたｎ型ＳｎＳ半導体のただ１つの実証例である。ｎ型ＳｎＳ半導体材料は現在このような状況にあり、ＳｎＳホモ接合型太陽電池ができていない。また、一部にＳｎＳを用いた太陽電池では、その変換効率も５％程度に留まっていた。このような状況からホモ接合ＳｎＳ太陽電池は、その作成がいまだになされていない。 However, there are only reported examples of SnS n-type in Non-Patent Document 1, Non-Patent Document 2, and the like. Non-Patent Document 1 is a research report of n-type SnS by a method of adding Pb to SnS. In this method, SnS 1-x Pb x shows n-type conversion when x> 20%, and toxic Pb Is used. On the other hand, Non-Patent Document 2 is an example of Sn-doped SnS by the present inventors showing n-type conduction. This report is only one demonstration example of an n-type SnS semiconductor made by doping with a halogen element. The n-type SnS semiconductor material is currently in such a situation, and a SnS homojunction solar cell has not been made. Moreover, in the solar cell using SnS for a part, the conversion efficiency has been limited to about 5%. Under such circumstances, homojunction SnS solar cells have not yet been made.
毒性元素／希少元素を用いない、ハロゲン元素をドープして作成された新たなｎ型ＳｎＳ半導体材料を提供する。 Provided is a new n-type SnS semiconductor material prepared by doping a halogen element without using a toxic element / rare element.
本発明のｎ型ＳｎＳ半導体は、ＳｎＳ（硫化スズ）にＢｒが添加されたことを特徴とする。 The n-type SnS semiconductor of the present invention is characterized in that Br is added to SnS (tin sulfide).
Ｂｒ（臭素）をドープ（添加）することにより、毒性元素／希少元素を用いないｎ型ＳｎＳ半導体材料を提供することが可能となる。 By doping (adding) Br (bromine), it is possible to provide an n-type SnS semiconductor material that does not use toxic elements / rare elements.
ＳｎＳにハロゲン元素をドープすることによるｎ型ＳｎＳの作成は、（１）ドープされるハロゲン元素と硫黄とのイオン半径の違いにより硫黄サイトへの置換の可否が変わり、ハロゲン元素の違いによりＳｎ欠陥の生成エンタルピー（Ｓｎ欠陥のできやすさ）が変わると考えられること、（２）Ｓｎ欠陥ができるとホールが生成するためハロゲン元素により生じた電子を打ち消す働きをすると考えられることなどから、今までにあまり研究がなされていなかった。また、ハロゲン元素を実際にドープしてみないとｎ型となるかどうかはわからなかった。 The creation of n-type SnS by doping halogen elements into SnS is as follows: (1) The possibility of substitution with sulfur sites varies depending on the ion radius difference between the doped halogen element and sulfur, and Sn defects depend on the difference in halogen elements. From the fact that the generation enthalpy (easiness of Sn defects) of the metal is considered to change, and (2) it is thought that when the Sn defects are formed, holes are generated, so that the electron generated by the halogen element is counteracted. There was not much research done. Moreover, it was not known whether it would be n-type without actually doping with a halogen element.
上述したように非特許文献２によるＣｌ添加したＳｎＳがｎ型伝導を示す事例のみが、ハロゲン元素をドープして作成されたｎ型ＳｎＳ半導体の実証例であり、非毒性元素や希少元素を必要としない事例であった。 As described above, only the case where Sn-added SnS added according to Non-Patent Document 2 exhibits n-type conduction is a demonstration example of an n-type SnS semiconductor prepared by doping with a halogen element, which requires a non-toxic element or a rare element. It was a case that did not.
なお、後述するようにＦ（フッ素）やＩ（ヨウ素）ではＳｎＳ結晶そのものがうまく構成できずｎ形ＳｎＳ半導体を作成できていない。
（実施例）
本発明のｎ型ＳｎＳ半導体の作成方法を図１に示す。
As will be described later, Sn (SnS) crystal itself cannot be successfully constructed with F (fluorine) or I (iodine), and an n-type SnS semiconductor cannot be produced.
(Example)
A method for producing an n-type SnS semiconductor of the present invention is shown in FIG.
試料を合成するにあたって秤量ならびに混合の際に空気中の水分や酸素などの影響を最小限にするため、作業は窒素置換グローブボックス(UNICO UN-650L)中で行った。 In order to minimize the influence of moisture and oxygen in the air during weighing and mixing in synthesizing the sample, the work was performed in a nitrogen-substituted glove box (UNICO UN-650L).
まず、図１に示すように、ＳおよびＳｎをそれぞれ秤量する。ＳｎはＳｎインゴットを切削して得た（ステップ１）。 First, as shown in FIG. 1, each of S and Sn is weighed. Sn was obtained by cutting a Sn ingot (step 1).
ここで、静電気などでボート型秤量皿に物質が付着してしまう分の秤量誤差を少なくするため、ボート型秤量皿をあらかじめ秤量するＳおよびＳｎで汚したものを利用した。 Here, in order to reduce the weighing error due to the substance adhering to the boat-type weighing pan due to static electricity or the like, the boat-type weighing pan previously soiled with S and Sn was used.
秤量したＳおよびＳｎを他のボード型秤量皿に移し混合した。(ステップ２） The weighed S and Sn were transferred to another board-type weighing pan and mixed. (Step 2)
次にドーパント材料を秤量した。ここでは、Ｂｒ（臭素）をドーパントとするため、安定的に所望の量を添加できるようにするためＳｎＢｒ２を用いた。(ステップ３） The dopant material was then weighed. Here, since Br (bromine) is used as a dopant, SnBr 2 was used so that a desired amount can be stably added. (Step 3)
ステップ２で混合したＳとＳｎと、ステップ３で秤量したＳｎＢｒ２とを石英管に入れ混合し、風船で封をし、窒素置換グローブボックスから取り出す（スッテプ４）。ここで窒素置換グローブボックスからこれら材料を入れた石英管を取り出す際に風船で封をするのは、なるべく大気に触れないようにするためである。したがってこの効果を奏する方法であれば、他の方法による封管でも構わない。 S and Sn mixed in Step 2 and SnBr 2 weighed in Step 3 are mixed in a quartz tube, sealed with a balloon, and taken out from the nitrogen-substituted glove box (Step 4). Here, when the quartz tube containing these materials is taken out from the nitrogen-substituted glove box, it is sealed with a balloon in order to avoid exposure to the atmosphere as much as possible. Therefore, any other method may be used as long as it is a method that exhibits this effect.
取り出した石英管を１０Ｐａ以下の真空中で封管する。（ステップ５） The extracted quartz tube is sealed in a vacuum of 10 Pa or less. (Step 5)
真空封管した石英管を電気炉にいれ、Ｓ、Ｓｎ、ＳｎＢｒ２の混合物を加熱し、Ｂｒ添加のＳｎＳを焼成した。この時、室温から５２０℃まで１２時間（１２Ｈ）かけて温度を上昇させた後、そこから５２０℃の温度を保ったままさらに１２時間（１２Ｈ）かけて焼成した。その後さらに３時間（３Ｈ）かけて５２０℃から２０℃まで冷却した。(ステップ６） The quartz tube sealed in a vacuum was placed in an electric furnace, and the mixture of S, Sn, and SnBr 2 was heated to sinter the Sn-added BrS. At this time, the temperature was raised from room temperature to 520 ° C. over 12 hours (12H), and then calcined for 12 hours (12H) while maintaining the temperature at 520 ° C. Thereafter, it was further cooled from 520 ° C. to 20 ° C. over 3 hours (3H). (Step 6)
ステップ６により得られたＢｒ添加ＳｎＳを取り出し、粉砕し粉末にした（ステップ７）。 The Br-added SnS obtained in Step 6 was taken out and pulverized into a powder (Step 7).
ステップ７により得られたＢｒ添加ＳｎＳの粉末を、放電プラズマ焼結法（ＳＰＳ：Ｓｐａｒｋ Ｐｌａｓｍａ Ｓｉｎｔｅｒｉｎｇ）を用い高密度焼結体を作製した（ステップ８）。 A high-density sintered body was produced from the Br-added SnS powder obtained in step 7 using a spark plasma sintering (SPS) method (step 8).
放電プラズマ焼結は機械的な加圧とパルス電流によるダイスへの加熱に加え、試料の自己発熱、粒子間の放電プラズマエネルギーによる加熱によって短時間で密度に偏りのない均一な焼結体の作製が可能な焼結法である。 In spark plasma sintering, in addition to mechanical pressurization and heating to the die by pulse current, a uniform sintered body with no bias in density is produced in a short time by self-heating of the sample and heating by discharge plasma energy between particles. This is a possible sintering method.
図２は放電プラズマ装置の概略を示す図である。図２の放電プラズマ焼結装置のダイスの内側をカーボンシートで覆ってカーボンシートの筒を構成し、カーボンシートの筒の内側に高密度焼結体とする材料（試料）を投入し、筒の上下からパンチではさみ、試料を加圧するとともに試料を加熱することにより高密度焼結体を作成することができる。 FIG. 2 is a diagram showing an outline of the discharge plasma apparatus. The inside of the die of the discharge plasma sintering apparatus of FIG. 2 is covered with a carbon sheet to form a cylinder of carbon sheet, and a material (sample) that is a high-density sintered body is placed inside the cylinder of the carbon sheet. A high-density sintered body can be produced by sandwiching with a punch from above and below, pressurizing the sample and heating the sample.
本実施例では、ステップ７で作成したＢｒ添加ＳｎＳの粉末を、１０〜１２Ｐａの真空中で加熱温度を６００℃、加熱時間を１２分（６分で昇温）、加圧を約３．５ｋＮの条件で焼結させた。この結果、いずれも相対密度が８０％以上の高密度焼結体試料を作製することができた。 In this example, the Br-added SnS powder prepared in Step 7 was heated in a vacuum of 10 to 12 Pa at a heating temperature of 600 ° C., a heating time of 12 minutes (heating up in 6 minutes), and a pressure of about 3.5 kN. Sintering was performed under the following conditions. As a result, a high-density sintered body sample having a relative density of 80% or more could be produced.
ステップ８により得られたＢｒ添加ＳｎＳ高密度焼結体試料でゼーベック係数測定を行った。Ｂｒの添加量を変えてこれらのＢｒ添加ＳｎＳ高密度焼結体試料のゼーベック係数の測定結果を図３に示す。図３において三角印がＢｒ添加ＳｎＳの測定結果を示す。なお、図３では比較対象として同様に作成、測定したＣｌ添加ＳｎＳについての結果も併記している（図３においては丸印がＣｌ添加ＳｎＳの結果を示す）。 The Seebeck coefficient was measured on the Br-added SnS high-density sintered body sample obtained in Step 8. FIG. 3 shows the measurement results of the Seebeck coefficient of these Br-added SnS high-density sintered compact samples while changing the amount of Br added. In FIG. 3, the triangle marks indicate the measurement results of Br-added SnS. FIG. 3 also shows the results of Cl addition SnS prepared and measured in the same manner as a comparison target (in FIG. 3, circles indicate the results of Cl addition SnS).
図３に示すようにＢｒを０．４ａｔ．％以上添加したＢｒ添加ＳｎＳでゼーベック係数（Ｓｅｅｂｅｃｋ ｃｏｅｆｆｉｃｉｅｎｔ）がマイナスの値となっておりｎ型化が実現されたことがわかる。またＣｌのケースと同じようにほぼ同じ添加量でゼーベック係数がマイナスになっていることが明らかとなった。なお、図３から明らかなようにＢｒ添加のＳｎＳは少なくとも０．４ａｔ．％以上〜１．０ａｔ．％以下の範囲においてＢｒ添加のＳｎＳがｎ型の特性を示すことがわかる。一方、０．４ａｔ．％よりもＢｒ添加が少ない範囲ではゼーベック係数がプラスとなっており、ｎ型の特性を帯びないことも明らかになった。 As shown in FIG. It can be seen that n-type conversion was realized because the Seebeck coefficient was negative for Br-added SnS added in an amount of at least%. It was also found that the Seebeck coefficient was negative at almost the same addition amount as in the case of Cl. As is apparent from FIG. 3, the Sn addition with Br added is at least 0.4 at. % To 1.0 at. It can be seen that Sn-added SnS exhibits n-type characteristics in the range of not more than%. On the other hand, 0.4 at. It has also been clarified that the Seebeck coefficient is positive in a range where Br addition is less than% and does not have n-type characteristics.
次にＢｒ添加ＳｎＳについて試料のＸＲＤ測定を行った。そのＸＲＤ測定結果を図４に示す。図４の上段は、単相ノンドープＳｎＳ（無添加ＳｎＳ）試料の、下段はＢｒを０．９５ａｔ．％添加した試料のＸＲＤパターンをそれぞれ示している。なお、Ｂｒ添加ＳｎＳのＸＲＤ測定は、ステップ８で得られた高密度焼結体を粉砕した粉末で行った。また、単相ノンドープＳｎＳ（無添加ＳｎＳ）もＢｒ添加ＳｎＳと同様に単相ノンドープＳｎＳの高密度焼結体作成し、それを粉砕した粉末でＸＲＤ測定を行った。 Next, the XRD measurement of the sample was performed for Br-added SnS. The XRD measurement results are shown in FIG. 4 shows a single-phase non-doped SnS (non-added SnS) sample, and the bottom shows Br of 0.95 at. The XRD pattern of the sample to which% is added is shown. Note that the XRD measurement of Br-added SnS was performed using a powder obtained by pulverizing the high-density sintered body obtained in Step 8. In addition, single-phase non-doped SnS (non-added SnS) was prepared as a high-density sintered body of single-phase non-doped SnS in the same manner as Br-added SnS, and XRD measurement was performed on the pulverized powder.
ここで、図４上段の無添加ＳｎＳ（純粋なＳｎＳ）のＸＲＤパターンに記載している３ケタの数字はＳｎＳの面指数を示している。図４上段のＸＲＤパターンの全てのピークがＳｎＳのそれぞれの面に帰属できることから、単相ができていることが明らかである。図４上段および下段を比較すると同じ位置にのみピークがあり、余計なピークが無いため、Ｂｒ０．９５ａｔ．％添加した試料（図４下段）も単相の試料が得られていることが明らかである。なお、このＸＲＤパターンの縦軸は対数スケール（ａ．ｕ．）である。 Here, the 3-digit number described in the XRD pattern of additive-free SnS (pure SnS) in the upper part of FIG. 4 indicates the SnS surface index. Since all the peaks of the XRD pattern in the upper part of FIG. 4 can be attributed to the respective surfaces of SnS, it is clear that a single phase is formed. 4 has a peak only at the same position and no extra peak, therefore, Br0.95 at. It is clear that a single-phase sample is obtained from the sample to which% is added (lower part of FIG. 4). The vertical axis of this XRD pattern is a logarithmic scale (au).
Ｂｒに代えてフッ素を用いて本実施例と同様の実験を行った場合の試料のＸＲＤパターンを図５に示す。フッ素添加した場合、ＳｎＳのピークの他に、ＳｎＳ２、Ｓｎ２Ｓｎ３のピークも見えている。このことは、ＳｎＳの多結晶がそもそも作成困難であることを示している。なお、図５におけるＸＲＤ測定は、Ｂｒ添加ＳｎＳと同様にフッ素添加ＳｎＳの高密度焼結体作成し、それを粉砕した粉末で行った。 FIG. 5 shows an XRD pattern of a sample in the case where the same experiment as in this example was performed using fluorine instead of Br. When fluorine is added, in addition to the SnS peak, peaks of SnS 2 and Sn 2 Sn 3 are also visible. This indicates that SnS polycrystals are difficult to produce in the first place. In addition, the XRD measurement in FIG. 5 was performed with the powder which made the high density sintered compact of the fluorine addition SnS similarly to Br addition SnS, and grind | pulverized it.
また、Ｂｒに代えてヨウ素を用いて本実施例と同様の実験を行った場合の試料のＸＲＤパターンを図６に示す。ヨウ素２乃至３％添加の場合は、ＳｎＳｌ２のピークが見えており、ＳｎＳの多結晶そのものでさえも作成が困難であることがわかる。また、ヨウ素１％添加のＸＲＤパターンでは異相は見受けられないものの実際の実験では石英管での加熱後、管内に析出物が認められるため単相が得られたとは判断できなかった。なお、図６におけるＸＲＤ測定は、Ｂｒ添加ＳｎＳ試料と同様にヨウ素添加ＳｎＳの高密度焼結体作成し、それを粉砕した粉末で行った。 Further, FIG. 6 shows an XRD pattern of a sample in the case where an experiment similar to that of the present example was performed using iodine instead of Br. When 2 to 3% of iodine is added, the SnSl 2 peak is visible, and it is found that even the SnS polycrystal itself is difficult to prepare. Further, although no heterogeneous phase was observed in the XRD pattern with 1% iodine added, it was not possible to judge that a single phase was obtained in the actual experiment because precipitates were observed in the tube after heating in the quartz tube. In addition, the XRD measurement in FIG. 6 was performed with the powder which made the high density sintered compact of the iodine addition SnS similarly to the Br addition SnS sample, and grind | pulverized it.
以上のことからも、本発明のＢｒ添加ＳｎＳ半導体は、数少ないｎ型ＳｎＳ半導体となる半導体材料であることがわかる。 From the above, it can be seen that the Br-added SnS semiconductor of the present invention is a semiconductor material that becomes a few n-type SnS semiconductors.
ノンドープのＳｎＳ半導体は一般にｐ型を示すことから、ｎ型を示す本発明のＢｒ添加ＳｎＳを用いれば、ホモ接合型ＳｎＳ太陽電池を実現が可能となる。ｐ型のノンドープのＳｎＳ半導体と本実施例に示すＢｒ添加ｎ型ＳｎＳ半導体とがｐｎ接合するように構成にされ、このｐｎ接合を備えた太陽電池を構成することにより、ホモ接合型ＳｎＳ太陽電池とすることが可能となる。 Since non-doped SnS semiconductors are generally p-type, a homojunction SnS solar cell can be realized by using the Br-doped SnS of the present invention showing n-type. The p-type non-doped SnS semiconductor and the Br-doped n-type SnS semiconductor shown in the present embodiment are configured to be pn-junction, and by forming a solar cell including this pn-junction, a homojunction-type SnS solar cell It becomes possible.
Claims (5)
The solar cell according to claim 4, comprising a non-doped SnS semiconductor, wherein the non-doped SnS semiconductor and the n-type SnS semiconductor are configured to form a pn junction, and the pn junction is provided.
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